CN115136042A

CN115136042A - Optical laminate and display device

Info

Publication number: CN115136042A
Application number: CN202180015287.3A
Authority: CN
Inventors: 柴田直也; 西村直弥; 井上俊
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-02-18
Filing date: 2021-02-05
Publication date: 2022-09-30
Also published as: US20220413188A1; JPWO2021166694A1; WO2021166694A1; JP7481425B2

Abstract

The invention provides an optical laminate having excellent stress resistance from the surface and a display device having the optical laminate. The optical laminate of the present invention comprises, in order: the surface protective layer, the 1 st adhesive layer, the light absorption anisotropic layer and the 2 nd adhesive layer, wherein the 1 st adhesive layer has an indentation elastic modulus larger than that of the light absorption anisotropic layer, the light absorption anisotropic layer is a layer formed from a light absorption anisotropic layer forming composition containing a liquid crystalline compound and a dichroic material, and the thickness of the light absorption anisotropic layer is less than 5 [ mu ] m.

Description

Optical laminate and display device

Technical Field

The present invention relates to an optical laminate and a display device.

Background

Conventionally, as a display device represented by an organic Electroluminescence (EL) display device, a display device having an optical laminate including a polarizer (light absorption anisotropic layer) has been widely used.

In recent years, foldable or rollable display devices have been developed, and optical laminates used in such display devices are required to be thin. For example, as one of methods for thinning an optical laminate, a method using an optical laminate including a polarizer (light-absorbing anisotropic layer) formed by applying a composition containing a dichroic material and a liquid crystalline compound is known (patent document 1).

Prior art documents

Patent literature

Patent document 1: international publication No. 2019/151334

Disclosure of Invention

Technical problem to be solved by the invention

The optical laminate may have a surface protective layer for protecting the surface thereof. The surface protective layer is a layer disposed on the outermost surface of the optical laminate, and is generally bonded to the light absorption anisotropic layer by an adhesive layer.

Here, a display device including an optical laminate may be operated by bringing a stylus or the like into contact with the surface protective layer. In this case, the following problems sometimes occur: the display performance is deteriorated due to the deformation of the light absorption anisotropic layer by the pressure of the stylus pen. Therefore, an optical laminate having excellent stress resistance from the surface is required.

The present inventors have studied an optical laminate obtained by bonding a polarizer (light absorption anisotropic layer) described in patent document 1 and a surface protective layer via an adhesive bonding layer, and as a result, it has been found that there is room for improvement due to insufficient pressure resistance from the surface.

Accordingly, an object of the present invention is to provide an optical laminate having excellent stress resistance from the surface, and a display device including the optical laminate.

Means for solving the technical problem

As a result of intensive studies to solve the above problems, the present inventors have found that, in an optical laminate comprising a surface protective layer, a1 st adhesive layer and a light-absorbing anisotropic layer in this order, when the indentation elastic modulus of the 1 st adhesive layer is larger than that of the light-absorbing anisotropic layer, an optical laminate having excellent pressure resistance from the surface can be obtained even in a thin film having a thickness of the light-absorbing anisotropic layer of less than 5 μm, and have completed the present invention.

That is, the present inventors have found that the above problems can be solved by the following configuration.

[1]

An optical stack comprising, in order: a surface protective layer, a1 st adhesive layer, a light absorption anisotropic layer, and a2 nd adhesive layer,

the 1 st adhesive layer has an indentation elastic modulus larger than that of the light absorption anisotropic layer,

the light absorption anisotropic layer is a layer formed from a light absorption anisotropic layer forming composition containing a liquid crystalline compound and a dichroic material,

the thickness of the light absorption anisotropic layer is less than 5 μm.

[2]

The optical laminate according to [1], wherein,

the thickness of the light absorption anisotropic layer is less than 3 μm.

[3]

The optical laminate according to [1] or [2],

the 1 st adhesive layer contains a polyvinyl alcohol adhesive.

[4]

The optical laminate according to [1] or [2],

the 1 st adhesive layer contains an ultraviolet curable adhesive.

[5]

The optical laminate according to any one of [1] to [4], wherein,

the thickness of the layer disposed between the 1 st adhesive layer and the 2 nd adhesive layer is 10 μm or less.

[6]

The optical laminate according to any one of [1] to [5],

the storage modulus of the 2 nd adhesive layer is 0.5MPa or more.

[7]

The optical laminate according to any one of [1] to [6],

the molar content of the radical polymerizable group in the composition for forming a light-absorbing anisotropic layer is 1.0mmol/g or more relative to the total solid content of the composition for forming a light-absorbing anisotropic layer.

[8]

The optical laminate according to any one of [1] to [7], further comprising:

a photo-alignment layer containing a polymer having a repeating unit containing a radical polymerizable group,

the photo-alignment layer is disposed in contact with a surface of the light absorption anisotropic layer.

[9]

The optical laminate according to any one of [1] to [8],

the light absorption anisotropic layer has a visible light average transmittance of 45% or more.

[10]

A display device having the optical laminate of any one of [1] to [9 ].

Effects of the invention

According to the present invention, an optical laminate having excellent stress resistance from the surface and a display device including the optical laminate can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of the laminate of the present invention.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range expressed by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the present specification, 1 kind of substance corresponding to each component may be used alone or 2 or more kinds may be used in combination for each component. Here, when 2 or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination unless otherwise specified.

In the present specification, "(meth) acrylate" is a label indicating "acrylate" or "methacrylate", "meth (acrylic acid)" is a label indicating "acrylic acid" or "methacrylic acid", and "(meth) acryloyl group" is a label indicating "acryloyl group" or "methacryloyl group".

[ optical layered body ]

The optical laminate of the present invention (hereinafter also referred to as "laminate of the present invention") has a surface protective layer, a1 st adhesive layer, a light-absorbing anisotropic layer, and a2 nd adhesive layer in this order. The 1 st adhesive layer has a higher indentation elastic modulus than the light absorption anisotropic layer. The light absorption anisotropic layer is formed from a light absorption anisotropic layer forming composition containing a liquid crystalline compound and a dichroic material. The thickness of the light absorption anisotropic layer is less than 5 μm.

The laminate of the present invention has excellent stress resistance from the surface. The reason for this is not clear, but is estimated to be as follows.

A display device including an optical laminate may be operated by bringing a stylus or the like into contact with the surface protective layer. In this case, the following problems sometimes occur: the display performance is deteriorated due to the deformation of the light absorption anisotropic layer by the pressure of the stylus pen.

As one of the methods for solving this problem, for example, a method of increasing the hardness of the surface protective layer may be considered, but the present inventors found that the deformation of the light absorption anisotropic layer cannot be sufficiently suppressed and the degradation of the display performance cannot be sufficiently suppressed only by increasing the hardness of the surface protective layer.

Therefore, the present inventors have conducted extensive studies and found that deformation of the light absorption anisotropic layer can be suppressed when the indentation elastic modulus of the 1 st adhesive bonding layer disposed between the surface protection layer and the light absorption anisotropic layer is larger than the indentation elastic modulus of the light absorption anisotropic layer.

The reason for this is presumed that the larger elastic modulus of the 1 st adhesive layer than the light absorption anisotropic layer plays a role of suppressing deformation of the light absorption anisotropic layer after the stress from the surface is transmitted to the light absorption anisotropic layer.

First, a laminate of the present invention will be described with reference to the drawings.

The laminate 100 shown in fig. 1 includes a surface protective layer 10, a1 st adhesive layer 20, a light absorption anisotropic layer 30, and a2 nd adhesive layer 40 in this order.

Here, the indentation elastic modulus of the 1 st adhesive bonding layer 20 is larger than the indentation elastic modulus of the light absorption anisotropic layer 30. And the thickness of the light absorption anisotropic layer 30 is less than 5 μm. The light absorption anisotropic layer 30 is a layer formed from a light absorption anisotropic layer forming composition containing a liquid crystalline compound and a dichroic material.

The laminate 100 may have a light alignment layer (not shown) so as to contact the surface of the light absorption anisotropic layer 30 opposite to the 1 st adhesive layer 20. That is, the photo-alignment layer is disposed between the light absorption anisotropic layer 30 and the 2 nd adhesive layer 40.

[ surface protective layer ]

The laminate of the present invention has a surface protective layer. The laminate of the present invention is used as a part of a display device, but preferably has a surface protective layer on the most visible side in this case.

The surface protective layer may be a layer composed of only 1 layer, or may be a layer in which 2 or more layers are stacked.

In the present invention, unless otherwise specified, the layer disposed on the opposite side of the light absorption anisotropic layer of the 1 st adhesive layer corresponds to the surface protective layer.

The surface protection layer is preferably high in hardness, but is also preferably high in recovery. Also, a low reflection layer that suppresses surface reflection generated in the air interface is also preferable.

As one preferable mode of the surface protective layer, a structure of a transparent support and a surface coating layer is assumed. The transparent support and the surface coating layer are described below.

< transparent support >

The term "transparent" as used herein means that the visible light average transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

As the transparent support, a plastic substrate is preferable.

Examples of the plastic constituting the plastic substrate include polyolefins such as polyethylene, polypropylene, and norbornene polymers; a cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates; a polyacrylate; cellulose esters such as triacetyl cellulose (TAC), diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; a polycarbonate; polysulfones; polyether sulfone; a polyether ketone; polyphenylene sulfide; polyphenylene ether, polyimide, and the like. Among them, cellulose ester, cycloolefin resin, polyethylene terephthalate, and polymethacrylate are particularly preferable from the viewpoint of being easily available on the market and having excellent transparency. From the viewpoint of flexibility, polyimide is preferable. Polyimide has a high refractive index and may have a large refractive index band gap, but it is also preferable to adjust the refractive index by a method of mixing silica particles or the like. The details of polyimide are disclosed in International publication No. 2018/062296 or International publication No. 2018/062190.

The thickness of the transparent support is preferably as thin as possible to maintain strength and workability from the viewpoint of quality to the extent that practical handling is possible and from the viewpoint that sufficient transparency can be secured.

The thickness of the transparent support is preferably 5 to 300 μm, and more preferably 5 to 100 μm.

When the laminate of the present invention is used as a circularly polarizing plate (particularly, when used as a circularly polarizing plate for mobile devices), the thickness of the transparent support is preferably about 5 to 50 μm.

< surface coating layer >

Examples of the surface coating layer include at least 1 selected from the group consisting of an antireflection layer, an antiglare layer, a hard coat layer, a mixed layer, and a scratch-resistant layer. They use known layer materials. In addition, these layers may be stacked in plural.

The antireflection layer is a structure that reduces reflection by a structure utilizing interference of light, unlike an antireflection plate called a circularly polarizing plate. As the simplest structure, the antireflection layer may be a structure composed of only a low refractive index layer. In order to further reduce the reflectance, it is preferable that the antireflection layer is configured by combining a high refractive index layer having a high refractive index and a low refractive index layer having a low refractive index. As a structural example, there is a structure in which a high refractive index layer/a low refractive index layer are formed in this order from the lower side, or a structure in which three layers having different refractive indexes are stacked in the order of a medium refractive index layer (a layer having a higher refractive index than the lower layer and a lower refractive index than the high refractive index layer)/a high refractive index layer/a low refractive index layer, and a structure in which a larger number of antireflection layers are stacked has been proposed. Among them, it is preferable to have a medium refractive index layer/a high refractive index layer/a low refractive index layer in this order on the hard coat layer from the viewpoint of durability, optical characteristics, cost, productivity, and the like, and examples thereof include those described in Japanese patent application laid-open Nos. 8-122504, 8-110401, 10-300902, 2002-243906, 2000-111706, and the like. Further, jp 2008-262187 a discloses an antireflection film having a three-layer structure and excellent durability against film thickness variations. When the antireflection film having the three-layer structure is provided on the surface of an image display device, the average value of the reflectance can be set to 0.5% or less, reflection can be reduced significantly, and an image having excellent three-dimensional appearance can be obtained. Further, other functions may be imparted to each layer, and examples thereof include a low refractive index layer having antifouling properties, a high refractive index layer having antistatic properties, a hard coat layer having antistatic properties, and a hard coat layer having antiglare properties (for example, japanese patent laid-open nos. 10-206603, 2002-243906, 2007-264113, and the like).

When the laminate of the present invention is applied to an organic EL display device for foldable (foldable) use, reference can be made to the description of jp 2018-56069 a as a layer constituting a surface coating layer. In an organic EL display device for foldable (foldable) use, since a cover glass cannot be used, a surface protective layer is required instead of the cover glass. For example, the following are described in paragraphs [0030] to [0040] of japanese patent application laid-open No. 2018-56069: a polyimide-based resin is preferable as the substrate having bendability capable of being bent preferably 20 ten thousand times, more preferably 30 ten thousand times, and further preferably 50 ten thousand times at a curvature radius of 3mm or less (e.g., 3mm, 2mm, 1 mm); the hard coat layer is preferably formed by blending an organic-inorganic hybrid material such as silica particles or a cage-like silsesquioxane compound with an ultraviolet-curable acrylic resin.

The surface coating preferably includes a hard coating layer using a silsesquioxane compound having a structure described in japanese patent application laid-open nos. 2015-212353 and 2017-008148.

As the mixed layer, a layer having a function of imparting adhesion between upper and lower layers, for example, a mixed layer described in international publication No. 2020/021931, can be used.

As the scratch-resistant layer, a layer for suppressing damage to the surface of the laminate, for example, a scratch-resistant layer described in international publication No. 2020/021931, can be used.

The thickness of the surface protective layer is not particularly limited, but is preferably 20 to 100 μm, more preferably 30 to 80 μm, and still more preferably 35 to 65 μm, from the viewpoint of further improving the effect of the present invention. Here, when the surface protective layer is composed of a plurality of layers, the thickness of the surface protective layer refers to the total thickness of the layers.

Here, the thickness of each layer in the laminate of the present invention is a value calculated based on an image obtained by observing a cross section of the laminate with a Scanning Electron Microscope (SEM), and is an arithmetic average of thicknesses at arbitrary 5 positions in each layer.

[1 st adhesive bonding layer ]

The laminate of the present invention has the 1 st adhesive bonding layer. In the present specification, the adhesive bonding layer means an adhesive layer made of an adhesive or an adhesive layer made of an adhesive.

In view of further improving the effect of the present invention, the 1 st adhesive layer is preferably an adhesive layer.

In the case where 2 or more adhesive bonding layers are provided between the surface protective layer and the optically-absorptive anisotropic layer, the 1 st adhesive bonding layer is the adhesive bonding layer closest to the optically-absorptive anisotropic layer among the 2 or more adhesive bonding layers.

The adhesive constituting the adhesive layer is not particularly limited, and is preferably a polyvinyl alcohol (PVA) -based adhesive or a curable adhesive in view of further improving the effect of the present invention. From the viewpoint of durability of the dichroic dye, a polyvinyl alcohol (PVA) -based adhesive having low oxygen permeability is more preferable.

The curable adhesive is preferably an active energy ray curable adhesive, and more preferably an Ultraviolet (UV) curable adhesive.

Examples of the UV curable adhesive include radical polymerization curable adhesives and cationic polymerization curable adhesives.

Examples of the radical polymerization curing adhesive include (meth) acrylate adhesives. Examples of the curable component in the (meth) acrylate adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group.

Examples of the cationically polymerizable curing adhesive include compounds having an epoxy group or an oxetane group. The compound having an epoxy group is not particularly limited as long as it has at least 2 epoxy groups in the molecule, and various curable epoxy compounds generally known can be used. Examples of the preferable epoxy compound include a compound having at least 2 epoxy groups and at least 1 aromatic ring in the molecule (aromatic epoxy compound), a compound having at least 2 epoxy groups in the molecule and at least 1 of which is formed between adjacent 2 carbon atoms constituting an alicyclic ring (alicyclic epoxy compound), and the like.

Examples of the adhesive constituting the adhesive layer include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinyl pyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives. Among them, acrylic adhesives (pressure-sensitive adhesives) are preferable from the viewpoint of transparency, weather resistance, heat resistance, and the like.

The thickness of the 1 st adhesive layer is not particularly limited, but is preferably 0.01 to 30 μm, more preferably 0.02 to 20 μm, and still more preferably 0.05 to 10 μm, from the viewpoint of further improving the effect of the present invention.

The indentation elastic modulus of the 1 st adhesive layer is not particularly limited as long as it is larger than the indentation elastic modulus of the light absorption anisotropic layer, but from the viewpoint of further excellent effects of the present invention, it is preferably 2 to 15GPa, more preferably 3 to 10GPa, and still more preferably 4 to 10 GPa.

In the present invention, the indentation elastic modulus of each layer means an elastic modulus measured by a nanoindentation method.

The elastic modulus can be measured by the nanoindenter method using, for example, a nanoindenter (trade name "Triboindenter TI-950", manufactured by Hysitron). In this measurement, the measurement mode was single indentation measurement, the measurement temperature was 25 ℃, the indenter was used as a cube corner indenter, the indentation load of the indenter on the measurement object was 50 μ N, the indentation speed of the indenter was 5 μm/sec, and the extraction speed of the indenter from the measurement object was 5 μm/sec. The derivation of the elastic modulus by nanoindentation was performed by the Oliver-Pharr method and by using a device. As for a specific derivation method, for example, as described in Hand book of Micro/nano tribody (second edition) Edited by Bharat Bhushan, CRCPRress (ISBN 0-8493-.

[ light absorption anisotropy layer ]

The laminate of the present invention has a light absorption anisotropic layer.

Here, the light absorption anisotropic layer is a light absorption anisotropic layer formed from a light absorption anisotropic layer forming composition (hereinafter, also referred to as a "liquid crystal composition") containing a liquid crystal compound and a dichroic material. From the reason that the effect of the present invention is more excellent, the light absorption anisotropic layer preferably does not contain iodine.

< composition for Forming light-absorbing Anisotropic layer (liquid Crystal composition) >

Hereinafter, components contained in the liquid crystal composition will be described.

(liquid Crystal Compound)

The liquid crystal composition contains a liquid crystalline compound. By containing the liquid crystalline compound, the dichroic material can be aligned with a high degree of alignment while suppressing deposition of the dichroic material.

The liquid crystalline compound is a liquid crystalline compound that does not exhibit dichroism.

As the liquid crystalline compound, any of a low molecular liquid crystalline compound and a high molecular liquid crystalline compound can be used. Here, the "low-molecular liquid crystalline compound" refers to a liquid crystalline compound having no repeating unit in its chemical structure. The "polymeric liquid crystalline compound" refers to a liquid crystalline compound having a repeating unit in its chemical structure.

Examples of the polymer liquid crystalline compound include thermotropic liquid crystalline polymers described in Japanese patent application laid-open No. 2011-237513. In addition, the polymeric liquid crystalline compound preferably has a crosslinkable group (polymerizable group) at the end from the viewpoint of excellent strength (particularly bending resistance) of the light-absorbing anisotropic layer. Examples of the crosslinkable group include polymerizable groups described in paragraphs [0040] to [0050] of Japanese patent application laid-open No. 2010-244038. Among these, from the viewpoint of improving reactivity and synthesis applicability, an acryloyl group, a methacryloyl group, an epoxy group, an oxetanyl group and a styryl group are preferable, and an acryloyl group and a methacryloyl group are more preferable.

Examples of the low-molecular liquid crystalline compound include those described in Japanese patent laid-open publication No. 2013-228706. The low-molecular liquid crystalline compound preferably has a crosslinkable group (polymerizable group) at the end. Specific examples of the crosslinkable group are as described above.

The content of the liquid crystalline compound is preferably 25 to 2000 parts by mass, more preferably 33 to 1000 parts by mass, and further preferably 50 to 500 parts by mass, based on 100 parts by mass of the dichroic material in the liquid crystal composition. When the content of the liquid crystalline compound is within the above range, the degree of orientation of the light absorption anisotropic layer is further improved.

The liquid crystalline compound may contain 1 kind alone, or 2 or more kinds. When 2 or more liquid crystalline compounds are contained, the content of the liquid crystalline compound refers to the total content of the liquid crystalline compounds.

From the reason that the effect of the present invention is more excellent, the liquid crystalline compound preferably contains a polymeric liquid crystalline compound having a repeating unit represented by the following formula (1L) (hereinafter, also referred to as "repeating unit (1L)").

[ chemical formula 1]

In the formula (1L), P1 represents a main chain of the repeating unit, L1 represents a single bond or a 2-valent linking group, SP1 represents a spacer group, M1 represents a mesogenic group, and T1 represents a terminal group.

Specific examples of the main chain of the repeating unit represented by P1 include groups represented by the following formulae (P1-A) to (P1-D), and among them, a group represented by the following formula (P1-A) is preferable from the viewpoint of the variety of monomers as raw materials and ease of handling.

[ chemical formula 2]

In formulae (P1-a) to (P1-D), "' indicates a bonding site to L1 in formula (1L). In the formulae (P1-A) to (P1-D), R ¹ 、R ² 、R ³ And R ⁴ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group may be a linear or branched alkyl group, or may be an alkyl group having a cyclic structure (cycloalkyl group). The number of carbon atoms of the alkyl group is preferably 1 to 5.

The group represented by the formula (P1-A) is preferably a unit of a partial structure of a poly (meth) acrylate obtained by polymerization of a (meth) acrylate.

The group represented by formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an epoxy group of a compound having an epoxy group.

The group represented by the formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetanyl group of a compound having an oxetanyl group.

The group represented by formula (P1-D) is preferably a siloxane unit of polysiloxane obtained by polycondensation of a compound having at least one group of an alkoxysilyl group and a silanol group. Examples of the compound having at least one of an alkoxysilyl group and a silanol group include compounds having the formula SiR ⁴ (OR ⁵ ) ₂ -compounds of the group represented. In the formula, R ⁴ And R in (P1-D) ⁴ A plurality of R are identical in meaning ⁵ Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

L1 represents a single bond or a 2-valent linking group.

Examples of the linking group having a valence of 2 represented by L1 include-C (O) O-, -OC (O) -, -O-, -S-, -C (O) NR ³ -、-NR ³ C(O)-、-SO ₂ -and-NR ³ R ⁴ -and the like. In the formula, R ³ And R ⁴ Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent W (described later).

When P1 is a group represented by the formula (P1-A), L1 is preferably a group represented by-C (O) O-, from the viewpoint that the effect of the present invention is more excellent.

When P1 is a group represented by any one of formulae (P1-B) to (P1-D), L1 is preferably a single bond, because the effect of the present invention is more excellent.

The spacer group represented by SP1 preferably includes at least 1 structure selected from the group consisting of an ethylene oxide structure, a propylene oxide structure, a polysiloxane structure and a fluorinated alkylene structure, for the reason of easy development of liquid crystallinity, availability of raw materials and the like.

Here, the ethylene oxide structure represented by SP1 is preferably — (CH) ₂ -CH ₂ O) _n1 A group represented by. Wherein n1 represents an integer of 1 to 20, and x represents a bonding position with L1 or M1 in the formula (1L). From the viewpoint of further improving the effect of the present invention, n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3.

Further, the propylene oxide structure represented by SP1 is preferably — (CH) for the reason that the effect of the present invention is more excellent ₃ )-CH ₂ O) _n2 A group represented by. In the formula, n2 represents an integer of 1 to 3, and denotes a bonding position with L1 or M1.

Further, from the reason that the effect of the present invention is more excellent, the polysiloxane structure represented by SP1 is preferably — (Si (CH) ₃ ) ₂ -O) _n3 -. Wherein n3 represents an integer of 6 to 10, and represents a bonding position with L1 or M1.

Further, the fluorinated alkylene structure represented by SP1 is preferably — (CF) for the reason that the effect of the present invention is more excellent ₂ -CF ₂ ) _n4 -. Wherein n4 represents an integer of 6 to 10, and represents a bonding position with L1 or M1.

The mesogenic group represented by M1 is a group representing the main skeleton of a liquid crystal molecule contributing to the formation of liquid crystal. The liquid crystal molecules exhibit liquid crystallinity in an intermediate state (mesophase) between a crystalline state and an isotropic liquid state. The mesogenic group is not particularly limited, and for example, reference can be made to "Flussie Kristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrial, Leipzig, journal of 1984), particularly the descriptions on pages 7 to 16, and the descriptions on the Committee for editing liquid crystal manuals, liquid crystal manuals (pill good, journal of 2000), particularly the description in chapter 3.

The mesogenic group is preferably a group having at least 1 cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group, for example.

From the viewpoint of the effect of the present invention being more excellent, the mesogenic group preferably has an aromatic hydrocarbon group, more preferably 2 to 4 aromatic hydrocarbon groups, and still more preferably 3 aromatic hydrocarbon groups.

The mesogenic group is preferably a group represented by the following formula (M1-A) or the following formula (M1-B), and more preferably a group represented by the following formula (M1-B), from the viewpoints of the development of liquid crystallinity, the adjustment of liquid crystal phase transition temperature, the availability of raw materials, and the suitability for synthesis, and from the viewpoint of further improving the effects of the present invention.

[ chemical formula 3]

In the formula (M1-A), A1 is a 2-valent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. These groups may be substituted with alkyl, fluorinated alkyl, alkoxy or a substituent W.

The 2-valent group represented by A1 is preferably a 4-to 6-membered ring. The 2-valent group represented by a1 may be a single ring or a condensed ring.

Indicates the bonding position to SP1 or T1.

Examples of the aromatic hydrocarbon group having a valence of 2 represented by a1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, tetracene-diyl, and the like, and from the viewpoint of the variety of designs of the mesogenic skeleton, the availability of raw materials, and the like, phenylene or naphthylene is preferable, and phenylene is more preferable.

The 2-valent heterocyclic group represented by a1 may be either aromatic or non-aromatic, and is preferably a 2-valent aromatic heterocyclic group in view of further improving the degree of orientation.

Examples of the atom other than carbon constituting the 2-valent aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. When the aromatic heterocyclic group has a plurality of ring-constituting atoms other than carbon, these atoms may be the same or different.

Specific examples of the 2-valent aromatic heterocyclic group include pyridylene (pyridine-diyl), pyridazine-diyl, imidazole-diyl, thienylene (thiophene-diyl), quinolylene (quinoline-diyl), isoquinolylene (isoquinoline-diyl), oxazole-diyl, thiazole-diyl, oxadiazole-diyl, benzothiazole-diyl, benzothiadiazole-diyl, phthalimide-diyl, thienothiazole-diyl, thiazolothiazole-diyl, thienothiophene-diyl and thienooxazole-diyl.

Specific examples of the alicyclic group having a valence of 2 represented by a1 include cyclopentylene and cyclohexylene.

In the formula (M1-A), a1 represents an integer of 1 to 10. When a1 is 2 or more, a plurality of a1 may be the same or different.

In the formula (M1-B), a2 and A3 each independently represent a 2-valent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. Specific examples and preferred modes of A2 and A3 are the same as those of A1 of the formula (M1-A), and therefore, descriptions thereof are omitted.

In the formula (M1-B), a2 represents an integer of 1 to 10, and when a2 is 2 or more, a plurality of a2 may be the same or different, a plurality of A3 may be the same or different, and a plurality of LA1 may be the same or different. From the reason that the effect of the present invention is more excellent, a2 is preferably an integer of 2 or more, more preferably 2.

In the formula (M1-B), LA1 is a linking group having a valence of 2 in the case where a2 is 1. When a2 is 2 or more, LA1 is each independently a single bond or a 2-valent linking group, and at least one of LA1 is a 2-valent linking group. When a2 is 2, it is preferable that one of 2 LA1 is a 2-valent linking group and the other is a single bond, because the effect of the present invention is more excellent.

In the formula (M1-B), examples of the 2-valent linking group represented by LA1 include-O-, - (CH) ₂ ) _g -、-(CF ₂ ) _g -、-Si(CH ₃ ) ₂ -、-(Si(CH ₃ ) ₂ O) _g -、-(OSi(CH ₃ ) ₂ ) _g - (g represents an integer of 1 to 10), -N (Z) -, -C (Z) -) ₂ -C(Z’) ₂ -, -C (O) -, -oc (O) -, -C (O) O-, -O — C (O) O-, -N (Z) C (O) -, -C (O) N (Z) -, -C (Z ') -C (O) O-, -O-C (O) - (Z) -, -C (Z) -, -N-, -N ═ C (Z) -, -C (Z') -O) N (Z ', -N (Z') -C (O) - (Z) -, -C (Z ') -C (O) -, -S-, -S-C (O) - (Z') -, -C (O) -, -S-C (Z ') -, -C (Z') -, -C (Z ') -C (O) -, -C (Z') -, -C (Z-) -C (O) -, -C (Z-) -C (C) S-) -S-) -S, -C (Z) ═ N ═ C (Z ') - (Z, Z', Z "independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group or a halogen atom, -C ≡ C-, -N ═ N-, -S- (O) -, - (O) S (O) O-, -O (O) S (O), sc- (O) -and-C (O) S-, etc. Among them, from the reason that the effect of the present invention is more excellent, it is preferably-C (O) O-. LA1 may be a combination of 2 or more of these groups.

Specific examples of M1 include the following structures. In the following specific examples, "Ac" represents an acetyl group.

[ chemical formula 4]

[ chemical formula 5]

Examples of the terminal group represented by T1 include a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms (ROC (O): R represents an alkyl group), an acyloxy group having 1 to 10 carbon atoms, an acylamino group having 1 to 10 carbon atoms, an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, an ureido group having 1 to 10 carbon atoms, a group containing a (meth) acryloyloxy group, and the like. Examples of the (meth) acryloyloxy group-containing group include groups represented by the formula-L-A (L represents a single bond or a linking group, and specific examples of the linking group are the same as those of the above-mentioned groups L1 and SP1, and A represents a (meth) acryloyloxy group).

From the viewpoint of further improving the effect of the present invention, T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and still more preferably a methoxy group. These terminal groups may be further substituted with these groups or the crosslinkable groups described above.

From the viewpoint of further improving the effect of the present invention, the number of atoms in the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 7. When the number of atoms of the main chain of T1 is 20 or less, the degree of orientation of the light absorption anisotropic layer is further improved. Here, the "main chain" in T1 means the longest molecular chain bonded to M1, and hydrogen atoms are not included in the number of atoms in the main chain of T1. For example, when T1 is an n-butyl group, the number of atoms in the main chain is 4, and when T1 is a sec-butyl group, the number of atoms in the main chain is 3.

From the reason that the effect of the present invention is more excellent, the content of the repeating unit (1L) is preferably 20 to 100% by mass based on 100% by mass of the total repeating units of the polymeric liquid crystalline compound.

In the present invention, the content of each repeating unit contained in the polymeric liquid crystalline compound is calculated from the charged amount (mass) of each monomer used for obtaining each repeating unit.

In the polymeric liquid crystalline compound, the repeating unit (1L) may include 1 kind alone, or 2 or more kinds. Among them, from the reason that the effect of the present invention is more excellent, it is preferable that the polymeric liquid crystalline substance contains 2 kinds of repeating units (1L).

When the liquid crystalline polymer compound includes 2 kinds of repeating units (1L), the end group represented by T1 is an alkoxy group in one (repeating unit a) and the end group represented by T1 is a group other than an alkoxy group in the other (repeating unit B), for the reason that the effect of the present invention is more excellent.

In the repeating unit B, the terminal group represented by T1 is preferably an alkoxycarbonyl group, a cyano group, or a group containing a (meth) acryloyloxy group, and more preferably an alkoxycarbonyl group or a cyano group, because the effect of the present invention is more excellent.

From the viewpoint of further improving the effect of the present invention, the ratio (A/B) of the content of the repeating unit A in the liquid crystalline polymer compound to the content of the repeating unit B in the liquid crystalline polymer compound is preferably 50/50 to 95/5, more preferably 60/40 to 93/7, and still more preferably 70/30 to 90/10.

The polymeric liquid crystalline compound may have a repeating unit (1L) and a repeating unit containing no mesogenic group. Examples of the repeating unit not containing a mesogenic group include a repeating unit in which M1 in formula (1L) is a single bond.

When the polymeric liquid crystalline compound has a repeating unit containing no mesogenic group, the content is preferably more than 0% by mass and 20% by mass or less with respect to 100% by mass of the total repeating unit of the polymeric liquid crystalline compound.

(weight average molecular weight)

The weight average molecular weight (Mw) of the polymeric liquid crystalline substance is preferably 1000 to 500000, more preferably 2000 to 300000, from the viewpoint of further improving the effect of the present invention. When the Mw of the polymeric liquid crystalline compound is within the above range, the polymeric liquid crystalline compound can be easily handled.

In particular, the weight average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably 10000 or more, and more preferably 10000 to 300000, from the viewpoint of suppressing cracks at the time of coating.

In view of temperature latitude of the orientation degree, the weight average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably less than 10000, and preferably 2000 or more and less than 10000.

Here, the weight average molecular weight and the number average molecular weight in the present invention are values measured by a Gel Permeation Chromatography (GPC) method.

Solvent (eluent): n-methyl pyrrolidone

Device name: TOSOH HLC-8220GPC

Column: 3 TOSOH TSKgelSuperAWM-H (6 mm. times.15 cm) were ligated and used

Column temperature: 25 deg.C

Sample concentration: 0.1% by mass

Flow rate: 0.35mL/min

Calibration curve: the calibration curve of 7 samples having Mw of 2800000 to 1050(Mw/Mn of 1.03 to 1.06) was used for TSK standard polystyrene manufactured by TOSOH CORPORATION

The substituent W in the present specification will be described.

Examples of the substituent W include an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, even more preferably 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, even more preferably 2 to 8 carbon atoms, such as a propargyl group and a 3-pentenyl group), an aryl group (preferably an alkynyl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and a 3-pentynyl group), an aryl group (preferably an alkynyl group having 2 to 12 carbon atoms, and even more preferably 6 to 20 carbon atoms), and a cyclohexyl group, Particularly preferred is an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a2, 6-diethylphenyl group, a3, 5-bistrifluoromethylphenyl group, a styryl group, a naphthyl group, and a biphenyl group, a substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, and an anilino group), an alkoxy group (preferably a carbon number of 1 to 20, more preferably a carbon number of 1 to 15, and for example, a methoxy group, an ethoxy group, and a butoxy group), an oxycarbonyl group (preferably a carbon number of 2 to 20, more preferably a carbon number of 2 to 15, and particularly preferably 2 to 10, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and a phenoxycarbonyl group), and the like, An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, an acetoxy group, a benzoyloxy group, an acryloyl group, a methacryloyl group, and the like), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, an acetylamino group, a benzoylamino group, and the like), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, a methoxycarbonylamino group, and the like), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, for example, a phenoxycarbonylamino group, and the like), a sulfonylamino group (preferably having 1 to 20 carbon atoms, a phenoxycarbonylamino group, and the like), More preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a methanesulfonylamino group, a benzenesulfonylamino group and the like), a sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group), a carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include an unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, and a phenylcarbamoyl group), an alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a methylthio group, an ethylthio group and the like), and, An arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, phenylthio group and the like), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, methanesulfonyl group and toluenesulfonyl group and the like), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, methanesulfinyl group and benzenesulfinyl group and the like), a ureido group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, unsubstituted ureido group, methylureido group, phenylureido group and the like), a phosphoric acid amido group (preferably having 1 to 20 carbon atoms, for example, phenylureido group and the like), a phosphoric acid amide group, More preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include diethylphosphoramidate and phenylphosphatamide), a hydroxyl group, a mercapto group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a cyano group, a nitro group, a hydroxamic acid group, a sulfinyl group, a hydrazine group, an imino group, an azo group, a hetero atom-containing cyclic group (preferably a hetero atom-containing cyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example a hetero atom-containing cyclic group having a nitrogen atom, an oxygen atom, a sulfur atom, and the like), for example, an epoxy group, an oxetanyl group, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholinyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, and the like), a silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms), Particularly preferred is a silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group, a triphenylsilyl group, and the like), a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

The liquid crystalline compound in the present invention may include a low molecular weight liquid crystalline compound represented by the following formula (LC) because the effect of the present invention is more excellent.

[ chemical formula 6]

Q1-SPL1-ML-SPL2-Q2 (LC)

In the formula (LC), Q1 and Q2 each independently represent a crosslinkable group or a terminal group, SPL1 and SPL2 each independently represent a spacer group, ML represents a mesogenic group, and at least one of Q1 and Q2 is a crosslinkable group (polymerizable group).

Since SPL1 and SPL2 each independently represent the same structure as SP1 in the above formula (1L), their descriptions are omitted.

ML represents the same structure as M1 in the above formula (1L), and therefore, the description thereof is omitted.

Q1 and Q2 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heterocyclic group (which may be referred to as a hetero atom-containing cyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an aryloxy group, a siloxy group, a hetero atom-containing epoxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an ammonium group, an amido group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heteroatom-containing cyclic thio group, a sulfamoyl group, a sulfo group, an alkanesulfonyl groupAryl or arylsulfinyl, alkyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heteroatom-containing cycloazo, imide, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, phosphonyl, silyl, hydrazino, ureido, boronic acid (-B (OH)) ₂ ) Phosphate group (-OPO (OH) ₂ ) Sulfate group (-OSO) ₃ H) Crosslinkable groups (polymerizable groups) represented by the following formulae (P1) to (P-30).

[ chemical formula 7]

In the above formulas (P-1) to (P-30), R ^P Represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heterocyclic group (which may be referred to as a hetero atom-containing cyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an aryloxy group, a siloxy group, a hetero atom-containing epoxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an ammonium group, an amido group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heteroatom-containing cyclic thio group, a sulfamoyl group, a sulfo group, an alkyl group or an arylsulfinyl group, Alkyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heteroatom-containing cyclic azo, imide, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, phosphonyl, silyl, hydrazino, ureido, boronic acid (-B (OH)) ₂ ) Phosphate group (-OPO (OH) ₂ ) Or sulfate group (-OSO) ₃ H) Plural R ^P Each may be the same or different.

As the crosslinkable group, a radical polymerizable group or a cation polymerizable group is preferable, and as the radical polymerizable group, a vinyl group represented by the formula (P-1), a butadienyl group represented by the formula (P-2), a (meth) acryloyloxy group represented by the formula (P-4), a (meth) acrylamide group represented by the formula (P-5), a vinyl acetate group represented by the formula (P-6), a fumarate group represented by the formula (P-7), a styrene group represented by the formula (P-8), a vinylpyrrolidone group represented by the formula (P-9), a maleic anhydride represented by the formula (P-11) and a maleimide group represented by the formula (P-12) are preferable, the vinyl ether group represented by the formula (P-18), the epoxy group represented by the formula (P-19) and the oxetanyl group represented by the formula (P-20) are preferable. Among them, a (meth) acryloyloxy group as a radical polymerizable group is particularly preferable.

Specific examples of the low-molecular liquid crystalline compound include the following structures, but the low-molecular liquid crystalline compound is not limited thereto.

[ chemical formula 8]

The liquid crystallinity of the low-molecular liquid crystalline compound may be either nematic or smectic. From the viewpoint of handling and manufacturing suitability, the temperature range in which liquid crystallinity is exhibited is preferably room temperature (23 ℃) to 300 ℃, more preferably 40 to 250 ℃.

(dichroic substance)

The liquid crystal composition contains a dichroic substance. In the present invention, a dichroic substance refers to a dye whose absorbance varies depending on the direction. By containing the dichroic material, the degree of alignment of the liquid crystal layer is improved.

The dichroic substance is not particularly limited, and examples thereof include a visible light absorbing substance (dichroic dye), a luminescent substance (fluorescent substance, phosphorescent substance), an ultraviolet absorbing substance, an infrared absorbing substance, a nonlinear optical substance, a carbon nanotube, an inorganic substance (e.g., quantum rod), and the like, and conventionally known dichroic substances (dichroic dye) can be used.

Specifically, for example, there may be mentioned sections [0067] to [0071] of Japanese patent laid-open publication No. 2013-228706, [0008] to [0026] of Japanese patent laid-open publication No. 2013-227532, [0008] to [0015] of Japanese patent laid-open publication No. 2013-209367, [0045] to [0058] of Japanese patent laid-open publication No. 2013-14883, sections [0012] to [0029] of Japanese patent laid-open publication No. 2013-109090, [0009] to [0017] of Japanese patent laid-open publication No. 2013-101328, [0051] to [0065] of Japanese patent laid-open publication No. 2013-37353, sections [0049] to [ 0023 ] of Japanese patent laid-open publication No. 0049-03036, sections [0016] to [0018] of Japanese patent laid-open publication No. 11-3050369 ], sections [ 0019 ] to [ 0001 ] to [ 00769 ] of Japanese patent laid-007242, 2010, and sections [ 007242 ] of Japanese patent laid-open publication No. 2010 [ 002242 ] 007242, and [ 007242 ] of Japanese patent laid-1060 ] 2010, paragraphs 2010 [ 007242, Dichroic substances described in paragraphs [0011] to [0025] of Japanese patent laid-open No. 2010-215846, paragraphs [0017] to [0069] of Japanese patent laid-open No. 2011-048311, paragraphs [0013] to [0133] of Japanese patent laid-open No. 2011-213610, paragraphs [0074] to [0246] of Japanese patent laid-open No. 2011-237513, paragraphs [0005] to [0051] of Japanese patent laid-open No. 2016-006502, paragraphs [0005] to [0041] of International publication No. 2016/060173, paragraphs [0008] to [0062] of International publication No. 2016/136561, paragraphs [0014] to [0033] of International publication No. 2017/154835, paragraphs [0014] to [0033] of International publication No. 2017/154695, paragraphs [0013] to [0037] of International publication No. 2017/195833, paragraphs [0014] to [0034] of International publication No. 2018/164252, and the like.

The dichroic substance may have a crosslinkable group (polymerizable group).

Specific examples of the crosslinkable group include a (meth) acryloyl group, an epoxy group, an oxetanyl group, and a styryl group, and among them, a (meth) acryloyl group is preferable.

The content of the dichroic substance is preferably 1 to 80% by mass, more preferably 2 to 70% by mass, and still more preferably 3 to 60% by mass, based on 100% by mass of the solid content in the liquid crystal composition, from the viewpoint of further improving the degree of orientation and further improving the heat resistance of the formed light absorbing anisotropic layer.

Preferred examples of the dichroic materials include the 1 st dichroic material, the 2 nd dichroic material, and the 3 rd dichroic material described below. The dichroic substance may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

1 st dichroic substance

The 1 st dichroic material is a dichroic material having a maximum absorption wavelength in a range of 560nm or more and 700nm or less (more preferably 560 to 650nm, and particularly preferably 560 to 640 nm).

The maximum absorption wavelength (nm) of the dichroic substance in the present specification is determined from the ultraviolet-visible light spectrum in the wavelength range of 380 to 800nm measured by a spectrophotometer using a solution in which the dichroic substance is dissolved in a good solvent.

The 1 st dichroic material is preferably a compound represented by formula (1).

[ chemical formula 9]

In the formula (1), Ar1 and Ar2 each independently represent an optionally substituted phenylene group or an optionally substituted naphthylene group, and are preferably phenylene groups from the viewpoint of further improving the effects of the present invention.

In the formula (1), R1 represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an acylamino group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureido group, an alkylphosphatamido group, an alkylimino group or an alkylsilyl group, which may have a substituent.

Examples of the substituted alkyl group in R1 include an alkyl group wherein the carbon atom is replaced by-O-, -CO-, -C (O) -O-, -O-C (O) -, -Si (CH) ₃ ) ₂ -O-Si(CH ₃ ) ₂ -、-N(R1’)-、-N(R1’)-CO-、-CO-N(R1’)-、-N(R1’)-C(O)-O-、-O-C(O)-N(R1’)--N (R1 ') -C (O) -N (R1 '), -CH ═ CH-, -C ≡ C-, -N ═ N-, -C (R1 ') ═ CH-C (O) -or-O-C (O) -O-substituted groups. 1 or more carbon atoms of the alkyl group may be substituted with the above-mentioned groups, or 2 or more carbon atoms may be substituted with the above-mentioned groups.

The number of carbon atoms of the alkyl group in R1 is preferably 1 to 20, more preferably 2 to 18, still more preferably 4 to 14, and particularly preferably 8 to 12.

The alkyl group in R1 may have any of a linear, branched, and cyclic structure, but is preferably linear or branched, and more preferably linear, in view of further improving the effect of the present invention.

When R1 is a group other than a hydrogen atom, the hydrogen atom of each group may be substituted by a halogen atom, nitro group, cyano group, -N (R1') ₂ Amino, -C (R1 ') ═ C (R1') -NO ₂ -C (R1 ') -C (R1 ') -CN or-C (R1 ') -C (CN) ₂ And (4) substitution. Each group may have 1 or more hydrogen atoms substituted with the above-mentioned group, or 2 or more hydrogen atoms substituted with the above-mentioned group.

R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. When a plurality of R1's are present in each group, they may be the same as or different from each other.

In the formula (1), R2 and R3 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkylamido group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamido group.

Examples of the alkyl group having a substituent in R2 and R3 include alkyl groups wherein the carbon atom is replaced by-O-, -S-, -C (O) -O-, -O-C (O) -, -C (O) -S-, -S-C (O) -, -Si (CH) and ₃ ) ₂ -O-Si(CH ₃ ) ₂ -, -NR2 '-, -NR 2' -CO-, -CO-NR2 '-, -NR 2' -C (O) -O-, -O-C (O) -NR2 '-, -NR 2' -C (O) -NR2 '-, -CH ═ CH-, -C ≡ C-, -N ≡ N-, -C (R2') ═ CH-C (O) -or-O-C (O) -O-substituted groups. 1 or more carbon atoms of the alkyl group may be substituted with the above-mentioned groups, or 2 or more carbon atoms may be substituted with the above-mentioned groups.

The alkyl group in R2 and R3 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

The alkyl group in R2 and R3 may have any of a linear, branched, and cyclic structure, but is preferably linear or branched, and more preferably linear, in view of further improving the effect of the present invention.

When R2 and R3 are groups other than hydrogen atom, the hydrogen atom of each group may be replaced by a halogen atom, nitro group, cyano group, -OH group, -N (R2') ₂ Amino, -C (R2 ') ═ C (R2') -NO ₂ 、-C(R2’)＝C(R2’)-CN、-C(R2’)＝C(CN) ₂ And (4) substitution. Each group may have 1 or more hydrogen atoms substituted with the above-mentioned group, or 2 or more hydrogen atoms substituted with the above-mentioned group.

R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. When a plurality of R2's are present in each group, they may be the same as or different from each other.

R2 and R3 may be bonded to each other to form a ring, or R2 or R3 may be bonded to Ar2 to form a ring.

In view of further improving the effect of the present invention, R1 is preferably an electron-withdrawing group, and R2 and R3 are preferably groups having low electron-donating property.

Specific examples of the group in which R1 is an electron-withdrawing group include R1, which includes an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylsulfinyl group, an alkylureido group, and an alkyl group in which carbon atoms are substituted with-C (O) -O-and-O-. As the alkyl group whose carbon atom is substituted by-C (O) -O-and-O-, a group represented by R11-C (O) -O-R12-O-is preferable. R11 represents a linear or branched alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), and R12 represents a linear or branched alkylene group having 1 to 20 carbon atoms (preferably 2 to 18 carbon atoms).

Specific examples of the case where R2 and R3 are groups having low electron donating property include groups having the following structures. In addition, the group having the following structure is represented in the formula (1) in a form including a nitrogen atom to which R2 and R3 are bonded.

[ chemical formula 10]

Specific examples of the 1 st dichroic material will be described below, but the present invention is not limited thereto.

[ chemical formula 11]

Dichroic substance No. 2

The 2 nd dichroic material is a dichroic material having a maximum absorption wavelength in a range of 455nm or more and less than 560nm (more preferably 455 to 555nm, and particularly preferably 455 to 550 nm).

In particular, when a1 st dichroic material having a maximum absorption wavelength of 560 to 700nm and a2 nd dichroic material having a maximum absorption wavelength of 455nm or more and less than 560nm are used, the color tone of the light absorption anisotropic layer can be easily adjusted.

The 2 nd dichroic material is preferably a compound represented by formula (2).

[ chemical formula 12]

In the formula (2), n represents 1 or 2, and is preferably 1 from the viewpoint of further improving the effect of the present invention.

In formula (2), Ar3, Ar4, and Ar5 each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a heterocyclic group which may have a substituent, but from the viewpoint of further improving the effects of the present invention, a phenylene group which may have a substituent is preferable.

The heterocyclic group may be either aromatic or non-aromatic.

Examples of the atom other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom. When the aromatic heterocyclic group has a plurality of ring-constituting atoms other than carbon, these atoms may be the same or different.

Specific examples of the aromatic heterocyclic group include pyridylene (pyridine-diyl), pyridazine-diyl, imidazole-diyl, thienylene (thiophene-diyl), quinolylene (quinoline-diyl), isoquinolylene (isoquinoline-diyl), oxazole-diyl, thiazole-diyl, oxadiazole-diyl, benzothiazole-diyl, benzothiadiazole-diyl, phthalimide-diyl, thienothiazole-diyl, thiazolothiazole-diyl, thienothiophene-diyl and thienooxazole-diyl.

In the formula (2), R4 is as defined as R1 in the formula (1).

In the formula (2), R5 and R6 are defined as R2 and R3 in the formula (1), respectively.

From the viewpoint of durability, R4 is preferably an electron-withdrawing group, and R5 and R6 are preferably groups having low electron-donating properties.

Among such groups, specific examples in the case where R4 is an electron-withdrawing group are the same as those in the case where R1 is an electron-withdrawing group, and specific examples in the case where R5 and R6 are groups having low electron-donating property are the same as those in the case where R2 and R3 are groups having low electron-donating property.

In particular, at least one of R5 and R6 is preferably a methyl group or an ethyl group, but from the viewpoint of further improving the effects of the present invention, at least one is more preferably a methyl group, and particularly preferably only one is a methyl group.

A specific example of the 2 nd dichroic material is shown, but the invention is not limited thereto.

[ chemical formula 13]

3 rd dichroic substance

The 3 rd dichroic material is a dichroic material having a maximum absorption wavelength in a range of 380nm or more and less than 455nm (more preferably 385 to 454 nm).

The 3 rd dichroic material is a dichroic material other than the 1 st dichroic material and the 2 nd dichroic material, and specifically has a different chemical structure from the 1 st dichroic material and the 2 nd dichroic material.

Specific examples of the 3 rd dichroic substance include compounds other than the 1 st dichroic substance and the 2 nd dichroic substance among compounds described as the compound represented by formula (1) described in international publication No. 2017/195833.

The molar content of the radical polymerizable group in the liquid crystal composition is preferably 0.5mmol/g or more, more preferably 1.0mmol/g or more, and still more preferably 1.5mmol/g or more, based on the total solid content of the liquid crystal composition. When the molar content is 1.0mmol/g or more, the effect of the present invention is more excellent because the deformation of the film is suppressed.

The upper limit of the molar content is not particularly limited, but is usually 3.0mmol/g or less.

Here, the molar content of the radical polymerizable group means a ratio of a total molar amount (mol) of the radical polymerizable groups contained in the liquid crystal composition to 1g of a solid content of the liquid crystal composition. The content (mass%), the molecular weight, and the chemical structure of the compound having a radical polymerizable group contained in the liquid crystal composition can be calculated.

Specific examples of the radical polymerizable group include a vinyl group, a butadienyl group, (meth) acryloyloxy group, (meth) acrylamide group, a vinyl acetate group, a fumarate group, a styrene group, a vinylpyrrolidone group, maleic anhydride, and a maleimide group. The radical polymerizable group is preferably contained in at least one of the liquid crystalline compound and the dichroic material.

< solvent >

From the viewpoint of properties and the like, the liquid crystal composition preferably contains a solvent.

Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrotol, and cyclopentylmethyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, and chlorotoluene), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, and diethyl carbonate), alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexane), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, and 1, 2-dimethoxyethane), cellosolve acetate esters, and cellosolve esters, Sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, etc.), heteroatom ring-containing compounds (e.g., pyridine, etc.), and water. These solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among these solvents, organic solvents are preferably used, and halocarbons and ketones are more preferably used, from the viewpoint of further improving the effect of the present invention.

When the liquid crystal composition contains a solvent, the content of the solvent is preferably 70 to 99.5% by mass, more preferably 80 to 99% by mass, and particularly preferably 85 to 98% by mass, based on the total mass of the liquid crystal composition, from the viewpoint of further improving the effect of the present invention.

< surface modifier >

The liquid crystal composition preferably contains a surface modifier (surfactant). The inclusion of the surface modifier can improve the smoothness of the coated surface, improve the degree of orientation, and suppress dishing and unevenness to improve the in-plane uniformity.

The surface modifier is preferably a surface modifier for horizontally orienting a liquid crystalline compound, and compounds (horizontal orientation agents) described in paragraphs 0253 to 0293 of Japanese patent laid-open publication No. 2011-237513 can be used. Furthermore, a fluoro (meth) acrylate polymer described in paragraphs [0018] to [0043] of Japanese patent application laid-open No. 2007-272185 can be used. As the surface modifier, other compounds may be used.

When the liquid crystal composition contains the surface modifier, the content of the surface modifier in the liquid crystal composition is preferably 0.1 to 2.0% by mass, and more preferably 0.1 to 1.0% by mass, based on the total solid content of the liquid crystal composition.

In the case where the light absorption anisotropic layer contains the surface modifier, the content of the surface modifier with respect to the total mass of the light absorption anisotropic layer is preferably the same as the content of the surface modifier with respect to the total solid content of the liquid crystal composition.

< polymerization initiator >

The liquid crystal composition preferably contains a polymerization initiator because the effect of the present invention is more excellent.

The polymerization initiator is not particularly limited, but is preferably a photopolymerization initiator which is a photosensitive compound.

As the photopolymerization initiator, various compounds can be used without particular limitation. Examples of the photopolymerization initiator include an α -carbonyl compound (each of the specifications of U.S. Pat. Nos. 2367661 and 2367670), an acyloin ether (each of the specifications of U.S. Pat. No. 2448828), an α -hydrocarbon-substituted aromatic acyloin compound (each of the specifications of U.S. Pat. No. 2722512), a polyquinone compound (each of the specifications of U.S. Pat. Nos. 3046127 and 2951758), a combination of triarylimidazole dimer and p-aminophenyl ketone (see, for example, the specification of U.S. Pat. No. 3549367), acridine and phenazine compounds (see, for example, Japanese patent application laid-open Nos. 60-105667 and 4239850), oxadiazole compounds (see, for example, the specification of U.S. Pat. No. 4212970), and acylphosphine oxide compounds (see, for example, Japanese patent publication No. 63-40799, Japanese patent publication No. 5-29234, Japanese patent application laid-open No. 10-95788, and Japanese patent application laid-open No. 10-29997).

As such a photopolymerization initiator, commercially available products can be used, and Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure OXE-01, and the like, which are manufactured by BASF corporation, can be mentioned.

When the liquid crystal composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 6% by mass, more preferably 0.5 to 4% by mass, based on the total solid content of the liquid crystal composition, from the viewpoint of further improving the effects of the present invention.

< method for Forming light-absorbing Anisotropic layer >

The method for forming the light-absorbing anisotropic layer using the liquid crystal composition is not particularly limited, and examples thereof include a method comprising the following steps in this order: a step of applying the liquid crystal composition onto a photo-alignment layer (for example, a photo-alignment layer described later) to form a coating film (hereinafter, also referred to as a "coating film forming step"); and a step of aligning the liquid crystalline component contained in the coating film (hereinafter, also referred to as "alignment step").

(coating film formation step)

The coating film forming step is a step of forming a coating film by applying the liquid crystal composition onto the photo-alignment layer.

By using a liquid crystal composition containing the above solvent or using a liquid material in which the liquid crystal composition is converted into a molten liquid or the like by heating or the like, the liquid crystal composition can be easily applied to the photo-alignment layer.

Specific examples of the method for applying the liquid crystal composition include known methods such as a roll coating method, a gravure printing method, a spin coating method, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, a spray coating method, and an ink jet method.

(alignment Process)

The alignment step is a step of aligning the liquid crystalline component contained in the coating film. Thus, a light absorption anisotropic layer can be obtained.

The liquid crystalline component is composed of: the dichroic material may contain a dichroic material having liquid crystallinity, in addition to the liquid crystalline compound, when the dichroic material has liquid crystallinity.

The orientation process may have a drying treatment. By the drying treatment, components such as a solvent can be removed from the coating film. The drying treatment may be performed by a method of leaving the coating film at room temperature for a predetermined time (for example, natural drying), or may be performed by a method of heating and/or blowing air.

Here, the liquid crystalline component contained in the liquid crystal composition may be aligned by the coating film forming step or the drying treatment. For example, in a mode in which a liquid crystal composition is prepared as a coating liquid containing a solvent, a coating film having light absorption anisotropy (i.e., a light absorption anisotropic layer) can be obtained by drying the coating film and removing the solvent from the coating film.

When the drying treatment is performed at a temperature not lower than the transition temperature at which the liquid crystalline component contained in the coating film is converted into the liquid crystal phase, the heating treatment described below may not be performed.

From the viewpoint of production applicability and the like, the transition temperature at which the liquid crystalline component contained in the coating film changes to a liquid crystal phase is preferably 10 to 250 ℃, and more preferably 25 to 190 ℃. When the transition temperature is 10 ℃ or higher, a cooling treatment for lowering the temperature to a temperature range in which the liquid crystal phase is formed is not necessary, and therefore, it is preferable. Further, if the transition temperature is 250 ℃ or lower, even when the liquid is once in an isotropic liquid state having a temperature higher than the temperature range in which the liquid crystal phase is present, the temperature is preferably not high, and waste of heat energy, deformation and deterioration of the substrate, and the like can be reduced.

The orientation step preferably includes a heat treatment. This enables the liquid crystalline component contained in the coating film to be aligned, and therefore the coating film after the heat treatment can be preferably used as a light-absorbing anisotropic layer.

From the viewpoint of manufacturing applicability, the heat treatment is preferably 10 to 250 ℃, and more preferably 25 to 190 ℃. The heating time is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds.

The orientation process may have a cooling process performed after the heating process. The cooling treatment is a treatment of cooling the heated coating film to about room temperature (20 to 25 ℃). This makes it possible to fix the alignment of the liquid crystalline component contained in the coating film. The cooling method is not particularly limited, and can be performed by a known method.

Through the above steps, the light absorption anisotropic layer can be obtained.

In this embodiment, the method of aligning the liquid crystalline component contained in the coating film includes, but is not limited to, drying treatment and heating treatment, and can be performed by known alignment treatment.

(other steps)

The method of forming the light absorption anisotropic layer may include a step of curing the light absorption anisotropic layer after the alignment step (hereinafter, also referred to as a "curing step").

For example, in the case where the light absorption anisotropic layer has a crosslinkable group (polymerizable group), the curing step is performed by heating and/or light irradiation (exposure). Among them, the curing step is preferably performed by light irradiation.

In addition, when the photo-alignment layer contains a compound having a photoreactive radical polymerizable group, unreacted radical polymerizable groups can be left on the surface of the photo-alignment layer by a method in which a radical polymerization initiator is not included in the photo-alignment layer, a method in which exposure is performed in an environment with a high oxygen concentration, or the like. By reacting the unreacted radical polymerizable group present on the surface of the photo-alignment layer with the radical polymerizable group of the light-absorbing anisotropic layer in the "curing step", the adhesion between the photo-alignment layer and the light-absorbing anisotropic layer can be improved.

The light source used for curing can be any of various light sources such as infrared light, visible light, and ultraviolet light, but ultraviolet light is preferred. In addition, when curing, ultraviolet rays may be irradiated while heating, or ultraviolet rays may be irradiated through a filter that transmits only a specific wavelength.

When the exposure is performed while heating, the heating temperature at the time of exposure depends on the transition temperature at which the liquid crystalline component contained in the light absorption anisotropic layer is converted into the liquid crystal phase, but is preferably 25 to 140 ℃.

Further, the exposure may be performed under a nitrogen atmosphere. In the case where the light absorbing anisotropic layer is cured by radical polymerization, inhibition of polymerization by oxygen is reduced, and therefore, it is preferable to perform exposure in a nitrogen atmosphere.

The thickness of the light absorption anisotropic layer is less than 5 μm, preferably 3 μm or less, and more preferably 2 μm or less.

Here, the present inventors found that, when the thickness of the light absorption anisotropic layer is less than 5 μm, the reduction in the stress resistance from the surface of the laminate is particularly significant, but the problem can be solved by using the laminate of the present invention.

The lower limit of the thickness of the light absorption anisotropic layer is preferably 0.1 μm or more, and more preferably 0.3 μm or more.

The indentation elastic modulus of the light absorption anisotropic layer is not particularly limited as long as it is smaller than the indentation elastic modulus of the 1 st adhesive layer, but from the viewpoint of further excellent effects of the present invention, it is preferably 0.1 to 5.0GPa, more preferably 0.5 to 3.5GPa, and further preferably 1 to 3 GPa.

The ratio of the indentation elastic modulus of the 1 st adhesive layer to the indentation elastic modulus of the light absorption anisotropic layer (indentation elastic modulus of the 1 st adhesive layer/indentation elastic modulus of the light absorption anisotropic layer) is greater than 1, but is preferably 1.5 or more from the viewpoint of further excellent effects of the present invention.

The upper limit of the above ratio (indentation elastic modulus of the 1 st adhesive layer/indentation elastic modulus of the light absorption anisotropic layer) is not particularly limited, but is preferably 10 or less from the viewpoint of further excellent effects of the present invention.

The visible light average transmittance of the light absorption anisotropic layer is preferably 45% or more, more preferably 48% or more, and further preferably 50% or more. The upper limit of the visible light average transmittance is 100%. The light absorption anisotropic layer has an average visible light transmittance of 45% or more, which is advantageous for improving the luminance.

In the present invention, the visible light average transmittance is an arithmetic average of transmittances in the visible light region (wavelength 400nm to 700nm) at intervals of 5 nm. A spectrophotometer (e.g., multichannel spectrometer (product name "QE 65000" manufactured by Ocean Optics, Inc.) is used to measure the transmittance.

[ alignment layer ]

The laminate of the present invention preferably has an alignment layer. Examples of the alignment layer include a photo-alignment layer and a rubbing alignment layer. Among them, the photo-alignment layer is preferable because the effect of the present invention is more excellent.

The alignment layer is preferably disposed in contact with a surface of the light absorption anisotropic layer.

From the viewpoint of the more excellent effect of the present invention, the thickness of the alignment layer is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm, and still more preferably 0.2 to 3 μm.

< photo-alignment layer >

The photo-alignment layer is a layer to which an alignment regulating force is imparted by light.

From the viewpoint of further improving the effects of the present invention, the photo-alignment layer preferably contains a polymer having a repeating unit containing a radical polymerizable group, and more preferably contains a copolymer of a repeating unit containing a radical polymerizable group and a repeating unit containing a cinnamoyl group. Specific examples of the radical polymerizable group include those described above, and among them, (meth) acryloyl is preferable.

From the viewpoint of further improving the effects of the present invention, the photo-alignment layer is preferably an alignment layer to which an alignment regulating force is applied, the alignment layer being obtained by performing the following steps: a step of applying a composition containing a compound having a photoreactive group (photoactive compound) (hereinafter, also simply referred to as "composition for forming a photo-alignment layer") onto a polymer film to form a coating film (coating film forming step); a step (drying step) of drying the coating film by heating; and a step (light irradiation step) of irradiating the dried coating film with polarized light or irradiating the surface of the coating film with unpolarized light from an oblique direction.

(coating film formation step)

As described above, the coating film forming step is a step of forming a coating film by applying the composition for forming a photo-alignment layer on a polymer film.

Polymeric films

The polymer film is not particularly limited, and a commonly used polymer film can be used.

Specific examples of the polymer constituting the polymer film include cellulose-based polymers; acrylic polymers having an acrylate polymer such as polymethyl methacrylate and polymers containing a lactone ring; a thermoplastic norbornene-based polymer; a polycarbonate-series polymer; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; a vinyl chloride polymer; amide polymers such as nylon and aromatic polyamide; an imide polymer; a sulfone-based polymer; a polyether sulfone-based polymer; a polyether ether ketone polymer; polyphenylene sulfide-based polymer; a vinylidene chloride polymer; a vinyl alcohol polymer; a vinyl butyral polymer; an aryl ester polymer; a polyoxymethylene polymer; an epoxy polymer; or a polymer obtained by mixing these polymers.

Among these, a cellulose-based polymer typified by triacetyl cellulose (hereinafter, also referred to as "cellulose acylate") can be preferably used.

Further, from the viewpoint of processability and optical properties, an acrylic polymer is also preferably used.

Examples of the acrylic polymer include polymethyl methacrylate and lactone ring-containing polymers described in paragraphs [0017] to [0107] of Japanese patent application laid-open No. 2009-98605.

In the present invention, in the aspect using a polymer film that can be peeled from the laminate produced, a cellulose-based polymer or a polyester-based polymer can be preferably used.

In the present invention, the polymer film is preferably transparent.

The thickness of the polymer film is not particularly limited, but is preferably 40 μm or less because the thickness of the laminate can be reduced. The lower limit is not particularly limited, but is usually 5 μm or more.

Photoactive compounds

As described above, the composition for forming a photo-alignment layer contains a compound having a photoreactive group (photoactive compound).

The photoreactive group refers to a group that generates liquid crystal alignment energy by irradiation with light. Specifically, the groups are groups which generate photoreaction, which is the origin of liquid crystal alignment energy, such as alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction of molecules (called photoactive compounds) by irradiation with light.

As the photoreactive group, a photoreactive group having an unsaturated bond, particularly a double bond is preferable from the viewpoint of further improving the effect of the present invention, and examples thereof include a group having at least one selected from the group consisting of a carbon-carbon double bond (C ═ C bond), a carbon-nitrogen double bond (C ═ N bond), a nitrogen-nitrogen double bond (N ═ N bond), and a carbon-oxygen double bond (C ═ O bond).

Examples of the photoreactive group having a C ═ C bond include a vinyl group, a polyene group, a stilbene group, a Stilbazolium group, a chalcone group, and a cinnamoyl group.

Examples of the photoreactive group having a C ═ N bond include groups having structures such as an aromatic schiff base and an aromatic hydrazine.

Examples of the photoreactive group having a C ═ O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group.

Examples of the photoreactive group having an N ═ N bond (hereinafter, also simply referred to as "azo group") include groups having an azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, bisazo group, and formazan group, and groups having azoxybenzene as a basic structure.

These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, or a haloalkyl group.

Among these groups, cinnamoyl group or azophenyl group is preferable because the irradiation amount of polarized light required for photo-alignment is relatively small and a photo-alignment layer excellent in thermal stability or stability over time is easily obtained.

(1) Preferred embodiment 1: photoactive compounds with azophenyl groups

The photoactive compound having an azophenyl group is particularly preferably a photoactive compound characterized by the following general formula (I).

General formula (I)

[ chemical formula 14]

In the formula, R ²¹ ～R ²⁴ Each independently represents a hydrogen atom or a substituent, wherein R ²¹ ～R ²⁴ At least one of the groups represents a carboxyl group or a sulfo group; m represents an integer of 1 to 4, n represents an integer of 1 to 4, o represents an integer of 1 to 5, p represents an integer of 1 to 5, and when m, n, o and p represent an integer of 2 or more, a plurality of R's are present ²¹ ～R ²⁴ May be the same or different.

In the general formula (I), as R ²¹ ～R ²⁴ The substituents represented by each of the above groups may be the following groups.

A carboxyl group (which may form a salt with an alkali metal, preferably a carboxyl group which may form an unformed salt or a sodium salt, more preferably a carboxyl group which may form a sodium salt), a sulfo group (which may form a salt with an alkali metal, preferably a sulfo group which may form an unformed salt or a sodium salt, more preferably a sulfo group which may form a sodium salt), an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group, etc.), an alkynyl group (preferably 2 to 20 carbon atoms, a sodium salt with an alkali metal, preferably a sulfo group, a sulfo group which may form an unformed salt with an unformed salt, or a sodium salt with an unformed salt, more preferably a sodium salt with an unformed salt), an unformed salt, an alkyl group (preferably a sulfo group, a carbon atom having 1 to 12, a carbon atom, a n-12 carbon atom, a n-decyl group, a cyclohexyl group, etc., a cyclohexyl group, etc., a cyclohexyl group, a, More preferably an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a propargyl group, a 3-pentynyl group and the like), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, a phenyl group, a2, 6-diethylphenyl group, a3, 5-bistrifluoromethylphenyl group, a naphthyl group, a biphenyl group and the like), a substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, an anilino group and the like),

An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, methoxy group, ethoxy group, butoxy group, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, acetoxy group, benzoyloxy group, etc.), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, acetylamino group, benzoylamino group, etc.), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, methoxycarbonylamino and the like), aryloxycarbonylamino (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, for example, phenoxycarbonylamino and the like), sulfonylamino (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino and the like), sulfamoyl (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like), carbamoyl (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, examples thereof include unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl and phenylcarbamoyl)

An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, methylthio group, ethylthio group, etc.), an arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, phenylthio group, etc.), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, methanesulfonyl group, toluenesulfonyl group, etc.), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, methanesulfinyl group, benzenesulfinyl group), a ureido group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, examples thereof include unsubstituted ureido, methylureido, phenylureido, etc.), phosphoramide (preferably having 1 to 20, more preferably having 1 to 10, even more preferably having 1 to 6, for example, diethylphosphoramide, phenylphosphonamide, etc.), hydroxyl, mercapto, halogen (for example, fluorine, chlorine, bromine, iodine), cyano, nitro, hydroxamic, sulfino, hydrazino, imino, heteroatom-containing cyclic group (preferably, a heteroatom-containing cyclic group having 1 to 30, more preferably 1 to 12 carbon atoms), a heteroatom-containing cyclic group having a nitrogen atom, oxygen, sulfur, etc., for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, etc.), etc, A silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group, a triphenylsilyl group, and the like).

These substituents may be further substituted with these substituents. And, in the case of having 2 or more substituentsThe same or different ones may be used. And, when possible, may bond to each other to form a ring. R is ²¹ ～R ²⁴ The group represented may be a polymerizable group or a substituent containing a polymerizable group.

In the general formula (I), as R ²¹ ～R ²⁴ The group represented by (a) is preferably a hydrogen atom, a carboxyl group, a sulfo group, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, an alkoxycarbonyl group, or a carbamoyl group, more preferably a hydrogen atom, a carboxyl group, a sulfo group, a halogen atom, a halomethyl group, a halomethoxy group, a cyano group, a nitro group, or a methoxycarbonyl group, and particularly preferably a hydrogen atom, a carboxyl group, a sulfo group, a halogen atom, a cyano group, or a nitro group, from the viewpoint of further improving the effects of the present invention.

R ²¹ ～R ²⁴ At least one of the groups represented is a carboxyl group or a sulfo group. The substitution position of the carboxyl group or the sulfo group is not particularly limited, but at least one R is preferable from the viewpoint of the photoactive effect ²¹ And/or at least one R ²² Is sulfo, more preferably at least one R ²¹ And at least one R ²² Is a sulfo group. From the same viewpoint, at least one R is preferred ²³ And/or at least one R ²⁴ Is a carboxyl group, more preferably at least one R ²³ And at least one R ²⁴ Is a carboxyl group. The carboxyl group is more preferably R in the meta-substituted azo group ²³ And R ²⁴ 。

In the general formula (I), m represents an integer of 1-4, n represents an integer of 1-4, o represents an integer of 1-5, and p represents an integer of 1-5. Preferably, m is an integer of 1 to 2, n is an integer of 1 to 2, o is an integer of 1 to 2, and p is an integer of 1 to 2.

Specific examples of the compound represented by the general formula (I) are given below, but the compound is not limited to the specific examples below.

[ chemical formula 15]

In the present invention, the compound having an azo group (particularly an azophenyl group) having a nitrogen-nitrogen double bond (N ═ N bond) is preferably a low-molecular-weight compound having no polymerizable group and having a molecular weight of 1000 or less, as represented by E-1 to E-17 described above, because of its excellent degree of orientation.

(2) Preferred embodiment 2: photoactive compounds having cinnamoyl groups

On the other hand, as the photoactive compound having a cinnamoyl group, a polymer is preferable because the influence due to contact of the photo-alignment layer is small.

Further, from the viewpoint of further reducing the influence of the contact of the photo-alignment layer, a polymer having a cinnamoyl group and a crosslinkable group is preferable.

The crosslinkable group may be any group that causes crosslinking reaction and crosslinks, and examples thereof include a cationic polymerizable group such as an epoxy group; and a radical polymerizable group such as acrylate and methacrylate.

On the other hand, in order to improve adhesion, it is more preferable that the hard coat layer of the photo-alignment layer has both a cationically polymerizable group and a radically polymerizable group in terms of being able to be used with a separating function.

As the polymer having a cinnamoyl group and a crosslinkable group, a photo-alignment copolymer having a repeating unit a including a cinnamoyl group represented by formula (a) below and a repeating unit B including a crosslinkable group represented by formula (B) below is preferably exemplified.

[ chemical formula 16]

In the above formula (A), R ¹ Represents a hydrogen atom or a methyl group. L is ¹ Represents a 2-valent linking group comprising a nitrogen atom and a cycloalkane ring, and a part of carbon atoms constituting the cycloalkane ring may be substituted with a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur.

R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Independently of one another represent hydrogen atomA substituent, R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Wherein adjacent 2 groups may be bonded to form a ring.

In the above formula (B), R ⁷ Represents a hydrogen atom or a methyl group, L ² Represents a linking group having a valence of 2, and X represents a crosslinkable group (polymerizable group).

In the present invention, by using a photo-alignment copolymer having a repeating unit a containing a cinnamoyl group represented by the formula (a) and a repeating unit B containing a crosslinkable group represented by the formula (B), the solvent resistance of the obtained photo-alignment layer and the alignment property of the polymeric liquid crystalline compound (hereinafter, simply referred to as "liquid crystal alignment property") when the photo-absorption anisotropic layer is formed are improved.

The details of this are not clear, but the present inventors presume as follows.

Namely, it is considered that L in the above formula (A) passes through ¹ The 2-valent linking group represented includes a nitrogen atom and a cycloalkane ring, and hydrogen bonding property and molecular rigidity are improved, so that molecular movement is suppressed, and as a result, solvent resistance is improved.

Similarly, it is considered that L in the above formula (A) passes through ¹ The 2-valent linking group represented by the formula (i) contains a nitrogen atom and a cycloalkane ring, and the glass transition temperature of the copolymer increases, so that the resulting photo-alignment layer has improved stability over time, and as a result, the liquid crystal alignment properties are improved regardless of the timing of forming the optically anisotropic layer.

Then, for L in the above formula (A) ¹ The 2-valent linking group comprising a nitrogen atom and a cycloalkane ring is illustrated. In the present invention, as described above, a part of the carbon atoms constituting the cycloalkane ring may be substituted with a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. Further, when a part of the carbon atoms constituting the cycloalkane ring has been substituted with a nitrogen atom, the nitrogen atom may not be independent of the cycloalkane ring.

And L in the above formula (A) ¹ The cycloalkane ring contained in the 2-valent linking group preferably has a C6 or higher cycloalkane ring as the one havingAs examples, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclododecane ring and the like can be given.

In the present invention, L in the above formula (A) is L for better liquid crystal alignment ¹ The linking group having a valence of 2 represented by any one of the following formulae (1) to (10) is preferable.

[ chemical formula 17]

In the formulae (1) to (10), 1 represents a bonding position to a carbon atom constituting the main chain in the formula (a), and 2 represents a bonding position to a carbon atom constituting the carbonyl group in the formula (a).

Among the 2-valent linking groups represented by any of the above formulae (1) to (10), the 2-valent linking group represented by any of the above formulae (2), (3), (7) and (8) is preferable from the viewpoint of improving the balance between the solubility in a solvent used in forming the photo-alignment layer and the solvent resistance of the resulting photo-alignment layer.

Then, for R in the above formula (A) ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ The substituent represented by the first embodiment of (1) is described. As described above, R in the above formula (A) ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ It may be a hydrogen atom instead of a substituent.

The reason why the cinnamoyl group easily interacts with the liquid crystalline compound and the liquid crystal alignment property is more favorable is considered that R in the formula (a) ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ The substituent(s) represented by one embodiment (b) is (are) preferably each independently a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, an amino group or a group represented by the following formula (11).

[ chemical formula 18]

Wherein in the formula (11), R represents a bonding position with the benzene ring in the formula (A) ⁹ Represents an organic group having a valence of 1.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.

As the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferred is an alkyl group having 1 to 6 carbon atoms as the linear alkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group and the like.

The branched alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include an isopropyl group, a tert-butyl group and the like.

The cyclic alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The linear haloalkyl group having 1 to 20 carbon atoms is preferably a fluoroalkyl group having 1 to 4 carbon atoms, and specific examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group and the like, and among them, a trifluoromethyl group is preferable.

The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 6 to 18 carbon atoms, and still more preferably an alkoxy group having 6 to 14 carbon atoms. Specifically, for example, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyloxy group and the like are preferable, and among these, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, and n-tetradecyloxy group are more preferable.

The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α -methylphenyl group, a naphthyl group and the like, and among them, a phenyl group is preferable.

The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include a phenoxy group, a 2-naphthoxy group and the like, and among them, a phenoxy group is preferable.

Examples of the amino group include a primary amino group (-NH) ₂ ) (ii) a Secondary amino groups such as methylamino; a tertiary amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, or a group having a nitrogen atom of a nitrogen-containing heterocyclic compound (e.g., pyrrolidine, piperidine, or piperazine) as a connecting bond.

The group represented by the above formula (11) is R in the above formula (11) ⁹ Examples of the 1-valent organic group include linear or cyclic alkyl groups having 1 to 20 carbon atoms.

The linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group, and among them, a methyl group and an ethyl group are preferable.

The cyclic alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like, and among them, a cyclohexyl group is preferable.

R in the above formula (11) is ⁹ The 1-valent organic group represented may be a group obtained by combining a plurality of the above-mentioned linear alkyl groups and cyclic alkyl groups directly or via a single bond.

In the present invention, R in the formula (a) is R because cinnamoyl group easily interacts with a liquid crystalline compound and liquid crystal alignment properties are more excellent ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Among them, at least R is preferable ⁴ The substituent is more preferably R because the obtained photo-alignment copolymer has improved linearity and is likely to interact with a liquid crystalline compound to further improve the liquid crystal alignment property ² 、R ³ 、R ⁵ And R ⁶ Both represent hydrogen atoms.

In the present invention, the reaction efficiency in the case of irradiating the obtained photo-alignment layer with light is obtainedFor the reason of improvement, R in the above formula (A) is preferably R ⁴ Are substituents which are electron donating.

Here, the electron donating substituent (electron donating group) means a substituent having a Hammett value (Hammett substituent constant σ p) of 0 or less, and examples thereof include an alkyl group, a haloalkyl group, an alkoxy group, and the like among the above substituents.

Among these, alkoxy groups are preferable, and alkoxy groups having 6 to 16 carbon atoms are more preferable, and alkoxy groups having 7 to 10 carbon atoms are even more preferable, from the viewpoint of further improving the liquid crystal alignment properties.

Next, L in the above formula (B) ² The 2-valent linking group shown is illustrative.

The 2-valent linking group is preferably a 2-valent linking group formed by combining at least 2 or more groups selected from the group consisting of a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms which may have a substituent, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (-O-), a carbonyl group (-C (-O-) and an imino group (-NH-) which may have a substituent, from the viewpoint that cinnamoyl group easily interacts with a liquid crystalline compound and the liquid crystal alignment properties are more excellent.

Examples of the substituent which the alkylene group, arylene group and imino group may have include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a carboxyl group, an alkoxycarbonyl group and a hydroxyl group.

The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, etc.), further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The alkoxy group is, for example, preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.), still more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

Examples of the aryl group include aryl groups having 6 to 12 carbon atoms, and specific examples thereof include phenyl, α -methylphenyl, naphthyl and the like, and among them, phenyl is preferable.

Examples of the aryloxy group include a phenoxy group, a naphthoxy group, an imidazolyloxy group, a benzimidazolyloxy group, a pyridin-4-yloxy group, a pyrimidyloxy group, a quinazolinyloxy group, a purinyloxy group, and a thiophen-3-yloxy group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the linear alkylene group include a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a decylene group, an undecylene group, a dodecenyl group, a tridecylene group, a tetradecylene group, a pentadecenyl group, a hexadecylene group, a heptadecenyl group, and an octadecenyl group.

Specific examples of the branched alkylene group include dimethylmethylene, methylethylene, 2-dimethylpropylene, and 2-ethyl-2-methylpropylene.

Specific examples of the cyclic alkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, exo-tetrahydrodicyclopentadiene-diyl, and the like, and among them, cyclohexylene is preferable.

Specific examples of the arylene group having 6 to 12 carbon atoms include phenylene, xylylene, biphenylene, naphthylene, and 2, 2' -methylenebisphenyl, and among them, phenylene is preferable.

Next, the crosslinkable group represented by X in the above formula (B) will be described.

Specific examples of X (crosslinkable group) in the formula (B) include an epoxy group, an epoxycyclohexyl group, an oxetanyl group, and a functional group having an ethylenically unsaturated double bond, and among them, at least one crosslinkable group selected from the group consisting of the following formulae (X1) to (X4) is preferable.

[ chemical formula 19]

In the formulae (X1) to (X4), L in the formula (B) is the same as L in the formula (B) ² Bonding position of R ⁸ Represents any of a hydrogen atom, a methyl group and an ethyl group, and in the formula (X4), S represents a functional group having an ethylenically unsaturated double bond.

Specific examples of the functional group having an ethylenically unsaturated double bond include a vinyl group, an allyl group, a styryl group, an acryloyl group, and a methacryloyl group, and an acryloyl group or a methacryloyl group is preferred.

In the present invention, it is preferable that the repeating unit B includes a repeating unit in which X in the formula (B) is a crosslinkable group represented by any one of the formulae (X1) to (X3) (hereinafter, also simply referred to as "repeating unit B1") and a repeating unit in which X in the formula (B) is a crosslinkable group represented by the formula (X4) (hereinafter, also simply referred to as "repeating unit B2") from the viewpoint of the high strength of the optical laminate obtained and the good handleability when another layer is formed using the optical laminate obtained.

Specific examples of the repeating unit a containing a cinnamoyl group represented by the formula (a) include repeating units a-1 to a-44 shown below. In the following formulae, Me represents a methyl group and Et represents an ethyl group. In the following specific examples, "1, 4-cyclohexyl" contained in the 2-valent linking group of the repeating units a-1 to a-10 may be either a cis-isomer or a trans-isomer, but is preferably a trans-isomer.

[ chemical formula 20]

On the other hand, as the repeating unit B (repeating unit B1) containing a crosslinkable group represented by the above formula (B), specific examples thereof include the following repeating units B-1 to B-17.

[ chemical formula 22]

Specific examples of the repeating unit B (repeating unit B2) containing a crosslinkable group represented by the formula (B) include the following repeating units B-18 to B-47.

[ chemical formula 23]

The content a of the repeating unit a and the content B of the repeating unit B in the photo-alignment copolymer satisfy the following formula (12), preferably the following formula (13), more preferably the following formula (14), and particularly preferably the following formula (15) in terms of a mass ratio.

0.03≤a/(a+b)≤0.5......(12)

0.03≤a/(a+b)≤0.3......(13)

0.03≤a/(a+b)≤0.2......(14)

0.05≤a/(a+b)≤0.2......(15)

In addition, in the case where the photo-alignment copolymer has the repeating unit B1 and the repeating unit B2, the content a of the repeating unit a, the content B1 of the repeating unit B1, and the content B2 of the repeating unit B2 preferably satisfy the following formula (16), more preferably satisfy the following formula (17), and further preferably satisfy the following formula (18) in terms of a mass ratio, from the viewpoint of maintaining good liquid crystal alignment properties and adhesion properties and further improving the strength of an optically anisotropic layer including a photo-alignment layer.

0.05≤b2/(a+b1+b2)≤0.7......(16)

0.10≤b2/(a+b1+b2)≤0.5......(17)

0.12≤b2/(a+b1+b2)≤0.35......(18)

The photo-alignment copolymer may have other repeating units in addition to the repeating units a and B, as long as the effects of the present invention are not hindered.

Examples of such a monomer (radical polymerizable monomer) forming another repeating unit include an acrylate compound, a methacrylate compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

The method for synthesizing the photo-alignment copolymer is not particularly limited, and for example, the photo-alignment copolymer can be synthesized by mixing a monomer forming the repeating unit a, a monomer forming the repeating unit B, and a monomer forming any other repeating unit, and polymerizing the mixture in an organic solvent using a radical polymerization initiator.

The weight average molecular weight (Mw) of the photo-alignment copolymer is preferably 10000 to 500000, more preferably 30000 to 300000, from the viewpoint of further improving the liquid crystal alignment.

When the photo-alignment copolymer is used, the content of the photo-alignment copolymer in the composition for forming a photo-alignment layer is not particularly limited, and when an organic solvent is contained, the content is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the organic solvent.

(additives)

The composition for forming a photo-alignment layer may contain 1 or more kinds of other additives other than the photoactive compound. For example, the additive is added for the purpose of adjusting the refractive index of the composition for forming a photo-alignment layer. As the additive, a compound having a hydrophilic group and a (meth) acryloyloxy group is preferable from the viewpoint of compatibility with the photoactive compound, and can be added to such an extent that the alignment energy is not significantly reduced. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, and the like.

(organic solvent)

The composition for forming a photo-alignment layer preferably contains an organic solvent from the viewpoint of workability in producing a photo-alignment layer.

Specific examples of the organic solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, etc.), these can be used alone, or can be used in combination of 2 or more.

The composition for forming a photo-alignment layer may contain other components than those described above, and examples thereof include a crosslinking catalyst (e.g., a thermally reactive acid generator), an adhesion improving agent, a leveling agent, a surfactant, and a plasticizer.

When an additive is used for the purpose of adjusting the refractive index of the composition for forming a photo-alignment layer, the refractive index of the additive is preferably 1.4 to 1.6, and more preferably 1.4 to 1.55.

In the present invention, it is preferable that the composition for forming a photo-alignment layer is a composition containing a compound having a photoreactive group and a crosslinkable group (for example, the photo-alignment copolymer described above) and not containing a radical polymerization initiator, from the viewpoint of the reason that the adhesiveness between the photo-alignment layer and the photo-absorption anisotropic layer is good.

(coating method)

As a method for applying the composition for forming a photo-alignment layer to the polymer film, for example, a known method such as a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, and a coater method, or a printing method such as a flexographic method is used.

When the optical laminate is produced by a Roll-to-Roll (Roll) continuous production method, a printing method such as a gravure coating method, a die coating method, or a flexographic method is generally used as a coating method.

(drying Process)

The method of drying the coating film formed in the coating step by heating is not particularly limited, and the drying temperature is preferably in the range of 50 to 180 ℃, and more preferably in the range of 80 to 150 ℃.

The drying time is preferably 10 seconds to 10 minutes, more preferably 30 seconds to 5 minutes.

When the composition for forming a photo-alignment layer contains a compound having a crosslinking catalyst such as a thermally reactive acid generator and a cationically polymerizable crosslinkable group, it is preferable that curing by a crosslinking reaction of the coating film is promoted by heat in this step.

(light irradiation step)

The polarized light to be irradiated to the coating film after the drying step is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, elliptically polarized light, and the like, and among them, linearly polarized light is preferable.

The "inclination direction" to which unpolarized light is irradiated is not particularly limited as long as it is a direction inclined by a polar angle θ (0 < θ < 90 °) with respect to the normal direction of the surface of the coating film, and may be appropriately selected according to the purpose, but θ is preferably 20 to 80 °.

In the present specification, "irradiation of linearly polarized light" and "irradiation of unpolarized light" are operations for causing a photoreaction of a photoactive compound. The wavelength of light used differs depending on the optically active compound used, and is not particularly limited as long as it is a wavelength required for the photoreaction. The peak wavelength of light used for light irradiation is preferably 200nm to 700nm, and more preferably ultraviolet light having a peak wavelength of light of 400nm or less.

Examples of the light source used for the light irradiation include commonly used light sources, and examples thereof include lamps such as a tungsten lamp, a halogen lamp, a xenon flash lamp, a mercury xenon lamp, and a carbon arc lamp, various lasers [ for example, a semiconductor laser, a helium-neon laser, an argon ion laser, a helium-cadmium laser, and a YAG (yttrium aluminum garnet) laser ], a light emitting diode, and a cathode ray tube.

As a method for obtaining linearly polarized light, a method using a polarizing plate (for example, an iodine polarizing plate, a dichroic dye polarizing plate, and a wire grid polarizing plate), a method using a reflective polarizer using a prism-based element (for example, a glan-thomson prism) or a brewster angle, or a method using light emitted from a laser light source having polarized light can be used. Further, only light of a desired wavelength may be selectively irradiated using a filter, a wavelength conversion element, or the like.

In the case where the irradiated light is linearly polarized light, a method of irradiating light perpendicularly or obliquely from the upper surface to the alignment layer or from the back surface to the alignment layer surface is employed. The incident angle of light differs depending on the optically active compound, and is preferably 0 to 90 ° (vertical), and more preferably 40 to 90 °.

In the case of unpolarized light, the alignment layer is obliquely irradiated with unpolarized light. The incident angle is preferably 10 to 80 degrees, more preferably 20 to 60 degrees, and further preferably 30 to 50 degrees.

The irradiation time is preferably 1 minute to 60 minutes, and more preferably 1 minute to 10 minutes.

When patterning is required, a method of irradiating light using a photomask a desired number of times in pattern formation or a method of writing a pattern by laser scanning can be employed.

< alignment layer for rubbing treatment >

The rubbing treatment alignment layer is a layer to which an alignment regulating force is applied by a rubbing treatment.

Many documents describe polymer materials used for rubbing alignment layers, and many commercially available products can be obtained. In the present invention, polyvinyl alcohol or polyimide and derivatives thereof are preferably used. For the alignment layer, reference is made to the description on page 43, line 24 to page 49, line 8 of International publication No. 01/88574A 1.

[2 nd adhesive layer ]

The laminate of the present invention has the 2 nd adhesive layer.

The 2 nd adhesive layer is disposed on the opposite side of the 1 st adhesive layer of the light absorption anisotropic layer.

In the case where 2 or more adhesive layers are provided between the light absorption anisotropic layer and the optically anisotropic layer described later, the 2 nd adhesive layer is an adhesive layer closest to the light absorption anisotropic layer among the 2 or more adhesive layers.

Specific examples of the material constituting the adhesive layer are described above, and therefore, the description thereof will be omitted.

The thickness of the 2 nd adhesive layer is not particularly limited, but is preferably 1 to 50 μm, more preferably 5 to 30 μm, and still more preferably 5 to 15 μm, from the viewpoint of further improving the effect of the present invention.

From the reason that the effect of the present invention is more excellent, the storage modulus of the 2 nd adhesive layer is preferably 0.5MPa or more, and more preferably 1MPa or more.

The storage modulus of the 2 nd adhesive layer is not particularly limited, and is preferably 10MPa or less, and more preferably 5MPa or less.

In the present invention, the storage modulus of the 2 nd adhesive layer is a value measured under the conditions of a frequency of 1Hz and 25 ℃ using a dynamic viscoelasticity measuring apparatus (DVA-200) manufactured by IT Keisoku Seigyo co.

In the laminate of the present invention, the thickness of the layer disposed between the 1 st adhesive layer and the 2 nd adhesive layer is preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 5 μm or less, from the viewpoint of more remarkable effects of the present invention. The lower limit of the thickness of the layer disposed between the 1 st adhesive layer and the 2 nd adhesive layer is equal to the thickness of the light absorption anisotropic layer.

[ optically anisotropic layer ]

The laminate of the present invention preferably has an optically anisotropic layer containing a liquid crystalline compound.

The optically anisotropic layer is preferably disposed on the opposite side of the light-absorbing anisotropic layer of the 2 nd adhesive layer.

The optically anisotropic layer is not particularly limited as long as it has optical anisotropy, but is preferably a retardation layer, and more preferably a λ/4 plate, in view of further excellent effects of the present invention.

Here, the "λ/4 plate" is a plate having a λ/4 function, specifically, a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).

Specific examples of the λ/4 plate include U.S. patent application publication No. 2015/0277006.

For example, a mode in which the λ/4 plate has a single-layer structure includes a stretched polymer film and a retardation film in which an optically anisotropic layer having a λ/4 function is provided on a support, and a mode in which the λ/4 plate has a multilayer structure includes a wide-band λ/4 plate in which a λ/4 plate and a λ/2 plate are laminated.

The λ/4 plate is preferably formed by coating a liquid crystal composition containing a liquid crystal compound, for the reason that the effect of the present invention is more excellent.

The retardation film provided with the optically anisotropic layer having a λ/4 function is more preferably a retardation film having 1 or more layers including at least one of liquid crystal compounds (discotic liquid crystals, rod-like liquid crystal compounds, and the like) formed by polymerizing liquid crystal monomers exhibiting a nematic liquid crystal layer or a smectic liquid crystal layer.

Further, as the λ/4 plate having excellent optical properties, a liquid crystalline compound having reverse wavelength dispersibility is preferably used. Specifically, a liquid crystalline compound of the general formula (II) described in international 2017/043438 can be preferably used. As for the method for producing a lambda/4 plate using a liquid crystalline compound having reverse wavelength dispersibility, reference can be made to the descriptions of examples 1 to 10 of International publication No. 2017/043438 or example 1 of Japanese patent application laid-open No. 2016-91022.

The thickness of the optically anisotropic layer (particularly, λ/4 plate) is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.5 to 5 μm, from the viewpoint of further improving the effect of the present invention.

[ solidified layer ]

The laminate of the present invention may have a cured layer having a thickness of 100nm or less for the purpose of reducing the refractive index difference between the light-absorbing anisotropic layer and its adjacent layers. The light-absorbing anisotropic layer preferably has the cured layer on the side opposite to the alignment layer (particularly, the photo-alignment layer).

In addition, in the case where the cured layer is disposed on the opposite side of the light absorption anisotropic layer of the 1 st adhesive layer, the cured layer corresponds to the surface protective layer.

Such a cured layer is not particularly limited, and various known cured layers can be used. For example, a layer containing a liquid crystalline compound or a layer obtained by curing a composition containing a polyfunctional monomer can be given. It is preferable to have a refractive index that can be matched with the refractive index of the optically anisotropic layer (particularly, the light absorption anisotropic layer).

[ oxygen barrier ]

The laminate of the present invention may have an oxygen barrier layer for the purpose of improving light resistance. It is preferable that the alignment layer (particularly, the photo-alignment layer) has an oxygen barrier layer on either one side or both sides of the side opposite to the photo-absorption anisotropic layer and the side opposite to the alignment layer (particularly, the photo-alignment layer) of the photo-absorption anisotropic layer. In the following description, the oxygen barrier layer provided on the side opposite to the light absorbing anisotropic layer of the alignment layer (particularly, the photo-alignment layer) is also referred to simply as "oxygen barrier layer 1", and the oxygen barrier layer provided on the side opposite to the alignment layer (particularly, the photo-alignment layer) of the light absorbing anisotropic layer is also referred to simply as "oxygen barrier layer 2".

In addition, in the case where the oxygen barrier layer is disposed on the opposite side of the light absorption anisotropic layer of the 1 st adhesive layer, the oxygen barrier layer corresponds to the surface protective layer.

The "oxygen barrier layer" refers to an oxygen barrier film having an oxygen barrier function, and specific examples thereof include layers containing organic compounds such as polyvinyl alcohol, polyethylene-vinyl alcohol, polyvinyl ether, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, cellulose ether, polyamide, polyimide, a styrene/maleic acid copolymer, gelatin, vinylidene chloride, and cellulose nanofibers.

In the present specification, the oxygen barrier function is not limited to a state in which oxygen is completely prevented from passing therethrough, and includes a state in which a small amount of oxygen passes therethrough in accordance with the target performance.

In the case where an oxygen barrier layer is provided on a transparent polymer film and a photo-alignment layer having an azobenzene compound represented by the general formula (I) is provided thereon, from the viewpoint of improving alignment properties, it is preferable to use polyvinyl alcohol having a saponification degree of 95 mol% or more or modified polyvinyl alcohol having a saponification degree of 95 mol% or more for the oxygen barrier layer.

Further, a thin layer made of a metal compound (metal compound thin layer) can be also exemplified. As for the method of forming the metal compound thin layer, any method can be used as long as it can form the target thin layer. For example, a sputtering method, a vacuum evaporation method, an ion plating method, a plasma CVD (Chemical Vapor Deposition) method, and the like are suitable, and specifically, the formation methods described in Japanese patent No. 3400324, Japanese patent application laid-open Nos. 2002-322561, and 2002-361774 can be adopted.

The component contained In the metal compound thin layer is not particularly limited as long as it can exert an oxygen barrier function, and for example, an oxide, nitride, or oxynitride containing 1 or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, or the like can be used. Among these, oxides, nitrides, or oxynitrides of metals selected from Si, Al, In, Sn, Zn, and Ti are preferable, and oxides, nitrides, or oxynitrides of metals selected from Si, Al, Sn, and Ti are particularly preferable. These may contain other elements as minor components.

Further, the oxygen barrier layer may be formed by laminating a layer containing the organic material and a thin layer of a metal compound, as described in, for example, U.S. Pat. No. 6413645, Japanese patent application laid-open No. 2015-226995, Japanese patent application laid-open No. 2013-202971, Japanese patent application laid-open No. 2003-335880, Japanese patent application laid-open No. 53-12953, and Japanese patent application laid-open No. 58-217344, or may be formed by mixing an organic compound and an inorganic compound, as described in, for example, International publication No. 2011/11836, Japanese patent application laid-open No. 2013-248832, and Japanese patent application laid-open No. 3855004.

The oxygen barrier layer may also serve as an alignment layer of an optically anisotropic layer having a λ/4 function. In this case, an oxygen barrier layer comprising polyvinyl alcohol, polyamide or polyimide is preferred.

In the case of a layer containing an organic compound, the thickness of the oxygen barrier layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5.5 μm, from the viewpoint of further improving the effect of the present invention. In the case of a thin metal compound layer, the thickness of the oxygen barrier layer is preferably 5nm to 500nm, more preferably 10nm to 200nm, from the viewpoint of further improving the effect of the present invention.

[ UV (ultraviolet) absorbing layer ]

The laminate of the present invention preferably has a functional layer (UV absorbing layer) having a function of reducing short-wavelength light on the surface protective layer side of the light absorbing anisotropic layer. By reducing the short-wave light, it is possible to provide a laminate excellent in light resistance by suppressing photodecomposition of a dichroic substance.

In one embodiment, the adhesive layer or the oxygen barrier layer preferably has a function of reducing short-wave light.

In another aspect, it is also preferable to newly provide a layer having a function of reducing short-wave light on the viewing side of the light absorption anisotropic layer.

The method of reducing the short-wave light is not particularly limited, and a method of utilizing light absorption by an absorbent or the like and a method of utilizing wavelength selective reflection by a multilayer film can be exemplified.

The short-wavelength light is light having a wavelength of 430nm or less. By reducing the light having a wavelength of 430nm or less, photodecomposition of the dye compound by sunlight or light from a light source used in the light resistance test in JIS B7751 and JIS B7754 can be suppressed.

Further, it is preferable that the transparent layer is transparent in a wavelength region of 450nm or more so as not to affect the performance of the light absorption anisotropic layer under visible light.

From the viewpoint of further improving the effect of the present invention, the UV absorbing layer is preferably a UV absorbing layer having an absorbance of 0.5 or more at a wavelength of 360nm and a wavelength of 400 nm.

[ display device ]

The display device of the present invention includes the laminate of the present invention. The display device is preferably an image display device capable of displaying images such as characters and graphics.

The display element used in the display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence display panel, a plasma display panel, and the like.

Among them, a liquid crystal cell or an organic EL display panel is preferable, and an organic EL display panel is more preferable. That is, the display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, an organic EL display device using an organic EL display panel as a display element, and more preferably an organic EL display device.

[ liquid Crystal display device ]

A liquid crystal display device as an example of the display device of the present invention is a liquid crystal display device having the optical laminate of the present invention (however, not including the λ/4 plate) and a liquid crystal cell.

In the present invention, among the optical layered bodies provided on both sides of the liquid crystal cell, the layered body of the present invention is preferably used as a polarizing element on the front side (viewing side), and more preferably used as a polarizing element on the front side and the rear side.

Hereinafter, a liquid crystal cell constituting the liquid crystal display device will be described in detail.

< liquid Crystal cell >

The liquid crystal cell used In the liquid crystal display device is preferably a VA (Vertical Alignment: Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching: In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited thereto.

In a TN mode liquid crystal cell, rod-like liquid crystalline molecules (rod-like liquid crystalline compounds) are aligned substantially horizontally when no voltage is applied, and further twisted at 60 to 120 degrees. TN mode liquid crystal cells are most widely used as color TFT liquid crystal display devices and are described in many documents.

In the VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. In addition to a narrow VA mode liquid crystal cell (described in japanese patent laid-open No. h 2-176625) in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and aligned substantially horizontally when a voltage is applied, a VA mode (Multi-domain Vertical Alignment) liquid crystal cell (described in SID97, Digest of tech. papers 28 (1997)) 845) in which the VA mode is Multi-domain for enlarging the angle of view, and a VA mode (n-ASM (Axially symmetric microcell) mode) in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and twisted Multi-domain Alignment is achieved when a voltage is applied (described in japanese patent laid-open No. 58 (59) - (1998)) and a narrow VA mode (liquid crystal display 98) in which the rod-like liquid crystal molecules are aligned substantially horizontally when a voltage is applied . Further, any of a PVA (Patterned Vertical Alignment) type, a photo-Alignment (Optical Alignment) type, and a PSA (Polymer-stabilized Alignment) type may be used. The details of these modes are described in detail in Japanese patent laid-open Nos. 2006-.

In the IPS mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially parallel to a substrate, and an electric field parallel to the substrate surface is applied to make the liquid crystal molecules respond in plane. In the IPS mode, black display is performed when no electric field is applied, and absorption axes of the upper and lower pair of polarizing plates are orthogonal to each other. Methods for improving the viewing angle by reducing light leakage in black display in an oblique direction using an optical compensation sheet are disclosed in japanese patent application laid-open nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[ organic EL display device ]

An organic EL display device, which is an example of the display device of the present invention, includes, for example, a system including the laminate (including a λ/4 plate) of the present invention and an organic EL display panel in this order from the viewing side.

The organic EL display panel is a display panel including organic EL elements in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure can be employed.

Examples

The present invention will be described in more detail with reference to the following examples. The materials, the amounts used, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the embodiments shown below.

Production example 1 and production example 3 are comparative examples, and production example 2 and production examples 4 to 22 are examples.

Production example 1

As the surface protection layer H1, a low reflection surface film CV-LC5 (supporting body was triacetyl cellulose, manufactured by FUJIFILM Corporation) was prepared.

[ production of laminate 1B ]

A laminate 1B in which the cellulose acylate film 1, the photo-alignment layer PA1, and the light-absorbing anisotropic layer P1 were sequentially formed was produced as follows.

< production of cellulose acylate film 1 >

(preparation of concentrated cellulose acylate solution for core layer)

The following composition was put into a mixing tank, and stirred to dissolve the respective components, thereby preparing a cellulose acetate solution for use as a core layer cellulose acylate dope.

Compound F

[ chemical formula 24]

(preparation of concentrated cellulose acylate solution for outer layer)

To 90 parts by mass of the above-mentioned core layer cellulose acylate dope was added 10 parts by mass of the following matting agent solution to prepare a cellulose acetate solution to be used as an outer layer cellulose acylate dope.

(production of cellulose acylate film 1)

After the core layer cellulose acylate dope and the outer layer cellulose acylate dope were filtered with a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, 3 layers of the core layer cellulose acylate dope and the outer layer cellulose acylate dopes on both sides thereof were simultaneously cast from a casting port onto a roll at 20 ℃ (a belt casting machine).

Subsequently, the film was peeled off with the solvent content of approximately 20 mass%, and both ends of the film in the width direction were fixed with a tenter jig, and dried while being stretched in the transverse direction at a stretch ratio of 1.1 times.

Then, the film was conveyed between the rolls of the heat treatment apparatus and further dried to produce an optical film having a thickness of 40 μm, which was used as the cellulose acylate film 1. The in-plane retardation of the resulting cellulose acylate film 1 was 0 nm.

< production of photo-alignment layer PA1 >

The coating liquid PA1 for forming an alignment layer, which will be described later, is continuously applied to the cellulose acylate film 1 by a wire bar. The support on which the coating film was formed was dried with warm air at 140 ℃ for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10mJ/cm2 using an ultra-high pressure mercury lamp) to form a photo-alignment layer PA1, thereby obtaining a TAC film with a photo-alignment layer. The film thickness of the photo-alignment layer PA1 was 0.3. mu.m.

Polymer PA-1

[ chemical formula 25]

Acid generator PAG-1

[ chemical formula 26]

Acid generator CPI-110F

[ chemical formula 27]

< formation of light-absorbing Anisotropic layer P1 >

The following composition for forming a light-absorbing anisotropic layer P1 was continuously applied to the obtained photo-alignment layer PA1 with a wire bar to form a coating layer P1.

Next, the coating layer P1 was heated at 140 ℃ for 30 seconds, and the coating layer P1 was cooled to room temperature (23 ℃).

Subsequently, the mixture was heated at 90 ℃ for 60 seconds and cooled again to room temperature.

Then, an LED lamp (center wavelength: 365nm) was used at an illuminance of 200mW/cm ² Was irradiated for 2 seconds under the irradiation conditions of (3), thereby producing a light absorption anisotropic layer P1 on the photo-alignment layer PA1, and this was used as a laminate 1B. The film thickness of the light absorption anisotropic layer P1 was 0.5. mu.m.

D-1

[ chemical formula 28]

D-2

[ chemical formula 29]

D-3

[ chemical formula 30]

Polymer liquid crystalline compound P-1

[ chemical formula 31]

Low-molecular liquid crystalline Compound M-1

[ chemical formula 32]

Surface modifier F-1

[ chemical formula 33]

< preparation of adhesive sheet N1 >

70 parts of butyl acrylate, 30 parts of methyl acrylate, 4 parts of acrylic acid, 2 parts of N, N-dimethyl methacrylamide, 0.1 part of azodiisobutyronitrile and 120 parts of ethyl acetate are added. This was polymerized by a solution polymerization method to obtain a solution of an acrylic copolymer having a weight average molecular weight of 150 ten thousand.

A solution prepared by mixing 3 parts by mass of CORONATE L (polyisocyanate, manufactured by Ltd., Nippon Polyurethane Industry Co., Ltd.), 0.2 part by mass of an aluminum chelate A (Kawaken Fine Chemicals Co., manufactured by Ltd., aluminum triacetylacetonate) and 0.1 part by mass of KBM-803(Shin-Etsu Chemical Co., manufactured by Ltd., manufactured by Gamma-mercaptopropylmethyldimethoxysilane) with 100 parts by mass of the solid content of the copolymer solution 1 was used as a binder composition N1. These compositions were applied to a separation membrane surface-treated with a silicone release agent using a die coater, and dried at 90 ℃ for 1 minute to produce an adhesive sheet N1 having an adhesive layer with a thickness of 5 μm. The storage modulus of the adhesive layer was 0.3 MPa.

[ production of laminate 1]

The light-absorbing anisotropic layer P1 side of the laminate 1B and the support 1 side of the surface protective layer H1 were bonded as a1 st adhesive layer using an adhesive SK2057 (S1, manufactured by Soken Chemical & Engineering co., ltd. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N1 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 1.

[ preparation example 2]

< preparation of UV adhesive S2 >

The following UV adhesive S2 was prepared.

CEL2021P

[ chemical formula 34]

CPI-100P

[ chemical formula 35]

< preparation of laminate 2 >

The light-absorbing anisotropic layer P1 side of the laminate 1B and the support 1 side of the surface protective layer H1 were bonded as a1 st adhesive layer using the UV adhesive S2 described above, and exposed to light at 1000mJ to cure. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N1 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 2.

[ preparation example 3]

The light-absorbing anisotropic layer P1 side of the laminate 1B and the support 1 side of the surface protective layer H1 were laminated using the UV adhesive S2 described above as a1 st adhesive layer, and cured by adjusting UV irradiation conditions so that the indentation elastic modulus of the 1 st adhesive layer became the value shown in table 2. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N1 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 3.

Production example 4

< production of adhesive sheets N2 and N3 >

The acrylate-based polymer A1 was prepared according to the following procedure.

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were polymerized by a solution polymerization method to obtain an acrylic polymer a1 having an average molecular weight of 200 ten thousand and a molecular weight distribution (Mw/Mn) of 3.0.

Next, using the obtained acrylate polymer a1, an acrylate adhesive was produced with the composition of table 1 below. These acrylate adhesives were applied to a separation film surface-treated with a silicone release agent using a die coater, dried at 90 ℃ for 1 minute, and irradiated with Ultraviolet (UV) rays under the following conditions to obtain adhesive sheets N2 and N3. However, UV irradiation was not performed in the production of the adhesive sheet N3. The composition of the acrylate adhesive, the film thickness of the adhesive sheet, and the storage modulus are shown in table 1 below.

(UV irradiation conditions)

Electrodeless lamp H bulb from Fusion

Illuminance 600mW/cm ² Light quantity 150mJ/cm ²

UV illuminance and light quantity were measured using "UVPF-36" manufactured by EYE GRAPHICS co.

[ Table 1]

(A) Multifunctional acrylate-based monomers: tris (acryloyloxyethyl) isocyanurate (molecular weight 423, 3-functional type) (manufactured by TOAGOSEI CO., LTD., trade name "ARONIX M-315")

(B) Photopolymerization initiator: mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1: 1, "IRGACURE 500" from Ciba Specialty Chemicals Co., Ltd "

(C) Isocyanate-based crosslinking agent: trimethylolpropane modified toluene diisocyanate

(Nippon Polyurethane Industry Co., Ltd. "CORONATE L" manufactured by Ltd.)

(D) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-403" manufactured by Ltd.)

< preparation of laminate 4 >

The light-absorbing anisotropic layer P1 side of the laminate 1B and the support 1 side of the surface protective layer H1 were laminated using the UV adhesive S2 described above as a1 st adhesive layer, and cured by adjusting UV irradiation conditions so that the indentation elastic modulus of the 1 st adhesive layer became the value shown in table 2. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N2 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 4.

[ preparation example 5]

The light absorption anisotropic layer P1 side of the laminate 1B and the support 1 side of the surface protective layer H1 were bonded as a1 st adhesive layer using the UV adhesive S2 described above, and cured by adjusting the UV irradiation conditions so that the indentation elastic modulus of the 1 st adhesive layer became the value shown in table 2. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N2 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 5.

[ preparation example 6]

(preparation of PVA adhesive S3)

20 parts by mass of methylolmelamine was dissolved in pure water at 30 ℃ per 100 parts by mass of an acetoacetyl group-containing polyvinyl alcohol resin (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetoacetylation: 5 mol%) to prepare an aqueous solution adjusted to a solid content concentration of 3.7% (PVA adhesive S3).

< preparation of laminate 6 >

The light-absorbing anisotropic layer P1 side of the laminate 1B and the support 1 side of the surface protection layer H1 were bonded to each other with the PVA adhesive S3 as the 1 st adhesive layer. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N2 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 6.

Production example 7

In the formation of the light-absorbing anisotropic layer of the laminated film 1B of preparation example 4, the composition P1 for forming a light-absorbing anisotropic layer was changed to the composition P2 shown below, thereby obtaining a laminate 7B. A laminate of production example 7 was obtained in the same manner as in production example 4, except that the laminate 7B was used instead of the laminate 1B.

D-5

[ chemical formula 36]

D-6

[ chemical formula 37]

[ preparation example 8]

[ production of surface protective layer H2 ]

As described below, a surface protection layer H2 was prepared in which the support 1, the hard coat layer, the mixed layer, and the scratch-resistant layer were formed in this order.

(production of polyimide powder)

832g of N, N-dimethylacetamide (DMAc) was charged into a 1L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature regulator, and a cooler under a nitrogen stream, and then the temperature of the reactor was set to 25 ℃. 64.046g (0.2mol) of bistrifluoromethylbenzidine (TFDB) was added thereto and dissolved. While maintaining the obtained solution at 25 ℃, 31.09g (0.07mol) of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 8.83g (0.03mol) of biphenyltetracarboxylic dianhydride (BPDA) were charged and reacted with stirring for a certain period of time. Then, 20.302g (0.1mol) of terephthaloyl chloride (TPC) was added to the solution to obtain a polyamic acid solution having a solid content of 13% by mass. Then, 25.6g of pyridine and 33.1g of acetic anhydride were put into the polyamic acid solution, and stirred for 30 minutes, further stirred at 70 ℃ for 1 hour, and then cooled to room temperature. 20L of methanol was added thereto, and the precipitated solid component was filtered and pulverized. Then, the resultant was dried in vacuum at 100 ℃ for 6 hours to obtain 111g of a polyimide powder.

< preparation of support 1 >

100g of the polyimide powder was dissolved in 670g of N, N-dimethylacetamide (DMAc) to obtain a 13 mass% solution. The resulting solution was cast onto a stainless steel plate and dried with hot air at 130 ℃ for 30 minutes. Then, the film was peeled off from the stainless steel plate, fixed to a frame by a pin, and the frame to which the film was fixed was put in a vacuum oven, heated for 2 hours while gradually raising the heating temperature from 100 ℃ to 300 ℃, and then gradually cooled. After separating the cooled film from the frame, the film was further heat-treated at 300 ℃ for 30 minutes as a final heat treatment step, thereby obtaining a support 1 made of a polyimide film and having a thickness of 30 μm.

< Synthesis of polyorganosilsesquioxane having polymerizability >

(Synthesis of Compound (A))

In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 297 mmol (73.2g) of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3 mmol (409mg) of methyltrimethoxysilane, 7.39g of triethylamine and 370g of MIBK (methyl isobutyl ketone) were mixed under a nitrogen flow, and 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel. The reaction solution was heated to 80 ℃ and subjected to polycondensation reaction under a nitrogen stream for 10 hours.

Then, the reaction solution was cooled, and 300g of 5 mass% saline was added to extract an organic layer. The organic layer was washed with 300g of 5 mass% saline solution and 300g of pure water 2 times in this order, and then concentrated under 1mmHg at 50 ℃ to obtain a MIBK solution having a solid content of 59.8 mass% and containing 59.0 mass% of a colorless and transparent liquid product { a polyorganosilsesquioxane compound (a) having an alicyclic epoxy group (Rb in the following (1): 2- (3, 4-epoxycyclohexyl) ethyl group, Rc: methyl group, a compound having q of 99, and r of 1) } in a solid content concentration.

[ chemical formula 38]

The number average molecular weight (Mn) of the obtained compound (A) was 2310, and the dispersity (Mw/Mn) was 2.1.

Further, 1mmHg was about 133.322 Pa.

(Synthesis of Polymer (1-1))

25.0g of t-amyl alcohol was placed in a 200-ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet, and the temperature was raised to 120 ℃. Subsequently, a mixed solution composed of 2- (perfluorohexyl) ethyl acrylate { corresponding to the monomer (K2) }3.25g (7.8 mmol), and a compound having the following structure (I-1) { corresponding to the monomer (K1) }2.26g (4.7 mmol), cyclohexanone 25.0g, and "V-601" (manufactured by Wako Pure Chemical Industries, Ltd.) 4.7g was uniformly dropped so that the dropping was completed within 120 minutes. After completion of the dropwise addition, the stirring was further continued for 3.5 hours to obtain 5.5g (solid content equivalent) of the polymer (1-1). The weight average molecular weight (Mw) of the polymer was 1,600.

[ chemical formula 39]

< preparation of composition for Forming hard coat layer >

(composition for Forming hard coat layer HC-1)

To the MIBK solution containing the compound (A), CPI-100P, the polymer (1-1) and MIBK (methyl isobutyl ketone) were added, and the concentrations of the respective components were adjusted to the following concentrations, and the mixture was charged into a mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4. mu.m, to obtain a composition HC-1 for forming a hard coat layer.

The compounds used in the composition for forming a hard coat layer are as follows.

CPI-100P: cationic photopolymerization initiator, San-Apro Ltd

< preparation of composition for Forming Mixed layer >

(composition M-1 for Forming Mixed layer)

The solvent of the MIBK solution containing the compound (a) was replaced with an MEK (methyl ethyl ketone) solution, DPHA, CPI-100P, IRGACURE127, leveling agent-1, and MEK were added, and the concentrations of the respective components were adjusted to the following concentrations, and the mixture was put into a mixing tank and stirred. The resulting composition was filtered through a polypropylene filter having a pore size of 0.4. mu.m, to obtain a composition M-1 for forming a mixed layer. In the mixed layer forming composition M-1, the mixing ratio of the compound (a) to DPHA is 50 mass%/50 mass% in the compound (a)/DPHA.

The compounds used in the composition for forming a mixed layer were as follows.

DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd

IRGACURE 127: radical photopolymerization initiator manufactured by BASF

Leveling agent-1: a polymer having the following structure (Mw: 20000, the composition ratio of the following repeating units is a mass ratio)

[ chemical formula 40]

< preparation of composition for Forming scratch-resistant layer >

(composition SR-1 for Forming scratch-resistant layer)

Each component was put into a mixing tank in the composition described below, stirred, and filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a scratch-resistant layer-forming composition SR-1.

Further, compounds used in the composition for forming a scratch resistant layer are as follows.

RS-90: lubricant, DIC Corporation

< preparation of surface protective layer H2 >

The composition HC-1 for forming a hard coat layer was applied to the support 1 by using a die coater. After drying at 120 deg.C for 1 minute, the resultant was irradiated at 25 deg.C with 18mW/cm of illumination intensity using an air-cooled mercury lamp ² The dose of irradiation was 10mJ/cm ² The hard coat layer is semi-cured by the ultraviolet rays of (1).

MEK was added to the mixed layer-forming composition M-1 to prepare a mixed layer-forming composition in which the solid content concentration was 1/10, and the mixed layer-forming composition was coated on the semi-cured hard coat layer using a die coater. After drying at 120 deg.C for 1 min, the resultant was irradiated with 18mW/cm of light at 25 deg.C and an oxygen concentration of 1% using an air-cooled mercury lamp ² The dose of irradiation was 10mJ/cm ² The mixed layer is semi-cured by the ultraviolet ray of (1), and the mixed layer is provided on the hard coat layer.

The scratch-resistant layer-forming composition SR-1 was applied onto the semi-cured mixed layer using a die coater. After drying at 120 deg.C for 1 minute, the resultant was irradiated with 60mW/cm of light using an air-cooled mercury lamp at 25 deg.C and an oxygen concentration of 100ppm ² The dose of irradiation was 800mJ/cm ² Further irradiated with an illuminance of 60mW/cm using an air-cooled mercury lamp under conditions of 80 ℃ and an oxygen concentration of 100ppm ² The dose of irradiation was 800mJ/cm ² Thereby completely curing the hard coat layer, the mixed layer, and the scratch resistant layer. Then, the obtained film was subjected toHeat treatment was carried out at 120 ℃ for 1 hour, whereby a surface protective layer H2 having a mixed layer having a thickness of 0.1 μm and a scratch-resistant layer having a thickness of 1.0 μm on a hard coat layer having a thickness of 11.0 μm was obtained.

The light-absorbing anisotropic layer P2 side of the laminate 1B and the support side of the surface protective layer H2 were laminated using the UV adhesive S2 described above as a1 st adhesive layer, and cured by adjusting UV irradiation conditions so that the indentation elastic modulus of the 1 st adhesive layer became the value shown in table 2. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N2 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 8.

Production example 9

In the formation of the light-absorbing anisotropic layer of the laminated film 1B of preparation example 6, the composition for forming a light-absorbing anisotropic layer P1 was changed to the composition for forming a light-absorbing anisotropic layer P3 shown below, and the thickness was changed from 0.5 μm to 1.5 μm, thereby obtaining a laminated body 9B. A laminate of production example 9 was obtained in the same manner as in production example 6, except that the laminate 9B was used instead of the laminate 1B.

D-4

[ chemical formula 41]

Production example 10

A laminate of production example 10 was obtained in the same manner as in production example 8, except that the laminate 9B was used in place of the laminate 1B in the formation of the light-absorbing anisotropic layer of the laminate film 1B of production example 8.

[ preparation example 11]

In the formation of the light-absorbing anisotropic layer of the laminated film 1B of production example 1, the following light-absorbing anisotropic layer-forming composition P4 was continuously applied to the above-mentioned photo-alignment layer PA1 with a wire bar to form a coating layer P4.

Subsequently, the coating layer P4 was heated at 120 ℃ for 60 seconds and rapidly cooled to room temperature (23 ℃) to form a dry film. In the dry film, the liquid crystal compound is a smectic B phase.

Then, an LED lamp (center wavelength: 365nm) was used at an illuminance of 200mW/cm ² Was irradiated for 2 seconds under the irradiation conditions of (3), thereby producing a light absorption anisotropic layer P4 on the photo-alignment layer PA1, and this was used as a laminate 11B. The film thickness of the light absorption anisotropic layer P1 was 2.5. mu.m.

A laminate of production example 11 was obtained in the same manner as in production example 8, except that the laminate 11B was used instead of the laminate 1B.

Dichroic dye D1

[ chemical formula 42]

Dichroic dye D2

[ chemical formula 43]

Dichroic dye D3

[ chemical formula 44]

Liquid crystalline compound M1 (mixed compound a/compound B75/25)

(Compound A)

[ chemical formula 45]

(Compound B)

[ chemical formula 46]

[ preparation example 12]

The laminate 11B was subjected to corona treatment on the light absorption anisotropic layer P4 side and the support side of the surface protective layer H1, respectively, and then bonded as the 1 st adhesive bonding layer using the PVA adhesive S3 described above. Thereafter, only the cellulose acylate film 1 was removed, and the pressure-sensitive adhesive sheet N2 was bonded as the removed surface to the 2 nd pressure-sensitive adhesive layer to obtain a laminate 12.

[ indentation elastic modulus ]

The indentation elastic modulus of each layer was measured in the manner described above.

[ storage modulus ]

The storage modulus of the 2 nd adhesive layer was measured as described above.

[ evaluation of stress resistance from surface ]

As an index of scratch resistance, pencil hardness evaluation described in JIS K-5400 was performed. The obtained laminates 1 to 14 were cut into a size of 50mm × 50mm, and the separation film was peeled off, and the adhesive layer 2 was pressure-bonded to a glass substrate (Eagle XG by Corning Incorporated co., ltd.). After conditioning them at 25 ℃ and 60% RH for 2 hours, the surface on which the hard coat layer was laminated was scratched with a 2H test pencil at a load of 4.9N. The laminate was laminated such that a polarizing plate (trade name: HCL2-5618HCS, manufactured by Dexerials Corporation) was arranged perpendicular to the absorption axis, and the portion rubbed with a pencil was visually observed on a backlight, and evaluated by the following judgment.

A: no light leakage

B: some light leakage was observed

C: significant light leakage was observed

The evaluation results are shown in table 2 below.

In table 2, "a/B" means a ratio of the indentation elastic modulus of the 1 st adhesive layer to the indentation elastic modulus of the light absorption anisotropic layer (indentation elastic modulus of the 1 st adhesive layer/indentation elastic modulus of the light absorption anisotropic layer).

As shown in table 2, in the laminate comprising the surface protective layer, the 1 st adhesive layer, the light absorption anisotropic layer, and the 2 nd adhesive layer in this order, when the indentation elastic modulus of the 1 st adhesive layer is larger than the indentation elastic modulus of the light absorption anisotropic layer, it is shown that the pressure resistance from the surface is excellent (production example 2, production examples 4 to 12).

On the other hand, when the indentation elastic modulus of the 1 st adhesive layer is equal to or less than the indentation elastic modulus of the light absorption anisotropic layer, the difference in the pressure resistance from the surface is shown (production examples 1 and 3).

From the comparison between production example 2 and production example 4, when the storage modulus of the 2 nd adhesive layer is 0.5MPa or more (production example 4), it is shown that the pressure resistance from the surface of the laminate is more excellent.

From the comparison between production example 4 and production example 7, it was found that the laminate was more excellent in the pressure resistance from the surface when the molar content of the radical polymerizable group in the compound contained in the composition for forming a light-absorbing anisotropic layer was 1.0mmol/g or more relative to the total solid content of the composition for forming a light-absorbing anisotropic layer (production example 4).

Production example 13

< production of optically Anisotropic layer >

(production of Positive A plate A1)

The coating liquid PA2 for forming an alignment layer, which will be described later, is continuously applied to the cellulose acylate film 1 by a wire bar. The support having the coating film formed thereon was dried with warm air at 140 ℃ for 120 seconds, and then the coating film was irradiated with polarized ultraviolet rays (10 mJ/cm) ² Ultra-high pressure mercury lamp) was used to form a 0.2 μm-thick photo-alignment layer PA2, thereby obtaining a tapeTAC film of photo-alignment layer.

Polymer PA-2

[ chemical formula 47]

Acid generator PAG-1

[ chemical formula 48]

The composition a-1 having the composition described later was applied to the photo-alignment layer PA2 using a bar coater. The coating film formed on the photo-alignment layer PA2 was heated to 120 ℃ with warm air and then cooled to 60 ℃, and then 100mJ/cm was measured at a wavelength of 365nm using a high-pressure mercury lamp under a nitrogen atmosphere ² Irradiating the coating film with ultraviolet rays, and heating the coating film to 120 ℃ while heating the coating film to 500mJ/cm ² The alignment of the liquid crystalline compound was fixed by irradiating the coating film with ultraviolet rays of (1) to produce a TAC film a1 having a positive a plate a 1.

The thickness of the positive A plate A1 was 2.5. mu.m, and Re (550) was 144 nm. The positive A plate A1 satisfies the relationship Re (450). ltoreq.Re (550). ltoreq.Re (650). Re (450)/Re (550) was 0.82.

Polymerizable liquid crystalline Compound L-1

[ chemical formula 49]

Polymerizable liquid crystalline Compound L-2

[ chemical formula 50]

Polymerizable liquid crystalline Compound L-3

[ chemical formula 51]

Polymerizable liquid crystalline Compound L-4

[ chemical formula 52]

Polymerization initiator PI-1

[ chemical formula 53]

Flatting agent T-1

[ chemical formula 54]

(production of Positive C plate C1)

As the temporary support, the cellulose acylate film 1 described above is used.

After the surface temperature of the cellulose acylate film 1 was raised to 40 ℃ by passing it through a dielectric heating roll having a temperature of 60 ℃, it was applied to one surface of the film at a coating weight of 14ml/m by means of a bar coater ² An alkaline solution of the composition shown below was applied and heated to 110 c and conveyed for 10 seconds under a steam-type far-infrared heater made by Noritake co.

Next, a film was coated with pure water at a rate of 3ml/m by using a bar coater in the same manner as above ² 。

Subsequently, water washing by a spray coater and dehydration by an air knife were repeated 3 times, and then the film was conveyed to a drying zone at 70 ℃ for 10 seconds to be dried, thereby producing an alkali saponification-treated cellulose acylate film 1.

The coating liquid 3 for forming an alignment layer having the following composition was continuously applied to the alkali-saponified cellulose acylate film 1 using a wire bar # 8. The obtained film was dried with 60 ℃ warm air for 60 seconds, and further dried with 100 ℃ warm air for 120 seconds to form an alignment layer.

The coating liquid C1 for forming a front C plate described later was applied to the alignment layer, and the obtained coating film was aged at 60 ℃ for 60 seconds and then used at 70mW/cm in air ² Irradiating the metal halide lamp (EYE GRAPHICS Co., Ltd.) with 1000mJ/cm ² The alignment state was fixed by ultraviolet rays of (2), and the liquid crystalline compound was vertically aligned to produce a positive C plate C1 having a thickness of 0.5 μm.

The resulting positive C plate had an Rth (550) of-60 nm.

[ chemical formula 55]

[ chemical formula 56]

[ chemical formula 57]

The above a and b represent the content (mass%) of each repeating unit with respect to all repeating units, a represents 90 mass%, and b represents 10 mass%.

< preparation of laminate of preparation example 13 >

The retardation side of the 2 nd adhesive layer and the positive a plate a1 was bonded to the laminate of production example 2.

At this time, the light absorption anisotropic layer was bonded so that the angle between the absorption axis of the light absorption anisotropic layer and the slow axis of the positive a plate a1 became 45 °.

Next, the alignment layer on the front a plate side and the cellulose acylate film 1 were removed, and the removed surface and the retardation side of the front C plate C1 were subjected to corona treatment, followed by bonding using the UV adhesive S2. The thickness of the UV adhesive layer was 1 μm.

The alignment layer on the front C-plate side and the cellulose acylate film 1 were removed, and the pressure-sensitive adhesive sheet N3 was bonded to the removed surface to prepare a laminate of preparation example 13.

< preparation of laminates according to preparation examples 14 to 22 >

Laminates of production examples 14 to 22 were produced in the same manner as in production example 13 for the laminates of production examples 4 to 12.

< production of organic EL display device >

GALAXY S4 manufactured by SAMSUNG co., ltd, on which an organic EL panel (organic EL display element) is mounted, is disassembled, the touch panel with the circularly polarizing plate is peeled from the organic EL display device, and the circularly polarizing plate is further peeled from the touch panel, so that the organic EL display element, the touch panel, and the circularly polarizing plate are separated individually. Next, the touch panel separated alone was bonded to the organic EL display element again, and the laminates of production examples 13 to 22 were further bonded to the touch panel so that the adhesive layer side became the panel side to produce an organic EL display device, and it was confirmed that the antireflection effect was exhibited.

Description of the symbols

10-surface protective layer, 20-1 st adhesive bonding layer, 30-light absorption anisotropic layer, 40-2 nd adhesive layer, 100-laminate.

Claims

1. An optical stack comprising, in order: a surface protective layer, a1 st adhesive layer, a light absorption anisotropic layer, and a2 nd adhesive layer,

the 1 st adhesive bonding layer has an indentation elastic modulus larger than that of the light absorption anisotropic layer,

the thickness of the light absorption anisotropic layer is less than 5 μm.

2. The optical stack of claim 1,

the thickness of the light absorption anisotropic layer is less than 3 μm.

3. The optical stack according to claim 1 or 2,

the 1 st adhesive bonding layer contains a polyvinyl alcohol-based adhesive.

4. The optical stack of claim 1 or 2,

the 1 st adhesive bonding layer contains an ultraviolet curing adhesive.

5. The optical stack according to any one of claims 1-4,

6. The optical stack according to any one of claims 1 to 5,

the storage modulus of the 2 nd adhesive layer is 0.5MPa or more.

7. The optical stack according to any one of claims 1 to 6,

8. The optical stack of any one of claims 1-7, wherein the optical stack further comprises:

a photo-alignment layer comprising a polymer having a repeating unit containing a radical polymerizable group,

the photo-alignment layer is configured to be in contact with a surface of the light-absorbing anisotropic layer.

9. The optical stack according to any one of claims 1 to 8,

10. A display device having the optical stack of any of claims 1-9.